Cationic reactive dyes

ABSTRACT

The cationic dyes of formula (1) specified in claim  1  are suitable especially for colouring keratin-containing fibres, more especially for colouring hair.

The present invention relates to a method of colouringkeratin-containing fibres using cationic imidazole dyes, to novelimidazole dyes and to a process for the preparation thereof.

There is already known from EP-A-714 954 a cationic imidazolazo dye thatis suitable for colouring hair and is obtained by diazotising4-alkoxyaniline, coupling with imidazole, then alkylating andquaternising, and finally reacting with p-phenylenediamine. That dyedoes not however, meet all the demands made in practice of such directhair dyes, its stability in aqueous solution, in particular, beingunsatisfactory.

It has now been found that that disadvantage can be overcome byacylating the free aromatic amino group of such dyes or replacing thatgroup with an alkoxy group. As a result the stability is appreciablyimproved and the dyes have adequate storage stability also at relativelyhigh pH values, for example at pH values of from 5 to 10, which is ofdecisive advantage especially for formulations for colouring hair.

The present invention accordingly relates to a method of colouringkeratin-containing fibres that comprises treating the fibres with a dyeof formula

wherein

-   Y₁ and Y₂ are each independently of the other hydrogen,    unsubstituted or substituted C₁-C₄alkyl, or halogen,-   R₁ and R₂ are each independently of the other hydrogen or    unsubstituted or substituted C₁-C₄alkyl,-   R₃ and R₄ are each independently of the other hydrogen,    unsubstituted or substituted C₁-C₄alkyl, C₁-C₄alkoxy or halogen,-   R₅ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or halogen,-   X is C₁-C₁₂alkoxy or a group of formula —N(R₆)—CO—R₇, wherein R⁶ is    hydrogen or C₁-C₄alkyl and R₇ is hydrogen, C₁-C₄alkyl or —NH₂ and-   A⁻ is an anion.

In accordance with the invention, alkyl radicals are to be understoodgenerally as open-chain or branched alkyl radicals, for example methyl,ethyl, n- and iso-propyl and n-, sec- and tert-butyl.

The alkyl radicals may be mono- or poly-substituted, for example byhydroxy, carboxy, halogen, cyano or C₁-C₄alkoxy.

The alkoxy radicals may contain from 1 to 12 carbon atoms, preferablyfrom 1 to 4 carbon atoms. They are, for example, methoxy, ethoxy,propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy orn-hexyloxy. The alkoxy groups, too, may be substituted, for example bythe radicals mentioned as possible substituents for the alkyl groups,especially by hydroxy or C₁-C₄alkoxy.

There come into consideration as anion A⁻ both inorganic and organicanions, for example halide, such as chloride, bromide or iodide,sulfate, hydrogen sulfate, methyl sulfate, boron tetrafluoride,aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, nitrate,benzenesulfonate, formate, acetate, propionate, lactate, and complexanions, such as an anion of a zinc chloride double salt.

The anion is generally governed by the preparation procedure.Preferably, chlorides, hydrogen sulfates, sulfates, methosulfates,phosphates, formates, lactates or acetates are present.

Halogen is to be understood as fluorine, bromine or iodine or,especially, chlorine.

Each of Y₁ and Y₂ is preferably methyl and especially hydrogen.

Each of R₁ and R₂ is preferably ethyl, hydroxyethyl or methyl.

R₃ and R₄ are preferably methoxy, methyl, hydrogen or chlorine.

The preferred meaning of R₅ is hydrogen.

X is preferably unsubstituted C₁-C₄alkoxy or a radical —NH—CO—R₇,wherein R₇ is especially hydrogen, methyl, ethyl or —NH₂.

Special preference is given in accordance with the invention to the useof dyes of formula

wherein

-   R₁ and R₂ are each methyl or ethyl,-   X is unsubstituted C₁-C₄alkoxy or a radical —NH—CO—R₇, wherein R₇ is    hydrogen, methyl, ethyl-   or —NH₂ and-   A⁻ is an anion.

The dyes of formula (2) are novel and the invention relates alsothereto.

The dyes of formulae (1) and (2) are prepared, for example, by acylatingthe free amino group in a compound of formula

wherein Y₁, Y₂, R₁, R₂, R₃, R₄, R₅ and A⁻ are as defined for formula(1), in a manner known per se. This is carried out, for example, byreaction with an appropriate acid, for example formic acid or aceticacid, an anhydride, for example acetic anhydride, or KOCN.

Compounds of formulae (1) and (2) wherein X is an alkoxy group areobtained, for example, by reacting a compound of formula

wherein Y₁, Y₂, R₁, R₂, R₃ and R₄ are as defined for formula (1) and R₈is C₁-C₄alkyl, with a p-alkoxy-aniline under reaction conditions knownper se.

The compounds of formulae (3) and (4) are known or can be obtained in amanner known per se.

The dyes of formulae (1) and (2) are suitable for colourngkeratin-containing fibres. “Keratin-containing fibres” are to beunderstood as wool, furs, feathers and, especially, human hair.

A prefered method of colouring keratin-containing fibres of the presentinvention comprises

-   a1) treating the fibres with a composition, possessing a pH value of    pH>7, and comprising a developing substance and at least one    coupling substance and an oxidation agent, or-   a2) treating the fibres with a composition, possessing a pH value of    pH<7, comprising a developing substance and at least one coupling    substance and an oxidation agent, or-   a3) treating the fibres with a dye of formula (1), or with a dye of    formula (4), or with a composition comprising a dye of formula (1),    and a composition, possessing a pH value of pH>7, and comprising a    developing substance and at least one coupling substance and an    oxidation agent, or-   a4) treating the fibres with a dye of formula (1) according to claim    1, or with a dye of formula (4), or with a composition comprising a    dye of formula (1), and a composition, possessing a pH value of    pH<7, and comprising a developing substance and at least one    coupling substance and an oxidation agent, and-   b) then applying without intermediary rinsing for 5 to 30 minutes,    and-   c1) then applying to the treated fibres a composition, possessing a    pH value of pH<7, and comprising a developing substance and at least    one coupling substance, or-   c2) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising a developing substance and at least    one coupling substance, or-   c3) then applying to the treated fibres a dye of formula (1)    according to claim 1, or a dye of formula (4) or a composition    comprising a dye of formula (1), and a composition, possessing a pH    value of pH<7, and comprising a developing substance and at least    one coupling substance, or-   c4) then applying to the treated fibres a dye of formula (1), or a    dye of formula (4), or a composition comprising a dye of formula    (1), and a composition, possessing a pH value of pH>7, and    comprising a developing substance and at least one coupling    substance, or-   c5) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising a dye of formula (1), or a    composition comprising a dye of formula (1), or-   c6) then applying to the treated fibres a composition, possessing a    pH value of pH<7, and comprising a dye of formula (1), or a    composition comprising a dye of formula (1), with the proviso that    least one dye of formula (1), or a composition comprising a dye of    formula (1), applied to the hair.

One preferred embodiment method of colouring keratin-containing fibrescomprises

-   a1) treating the fibres with a composition, possessing a pH value of    pH>7, and comprising a developing substance and at least one    coupling substance and an oxidation agent, or-   a2) treating the fibres with a composition, possessing a pH value of    pH<7, comprising a developing substance and at least one coupling    substance and an oxidation agent, and-   b) then applying without intermediary rinsing for 5 to 30 minutes,    and-   c3) then applying to the treated fibres a dye of formula (1)    according to claim 1, or a dye of formula (4) or a composition    comprising a dye of formula (1), and a composition, possessing a pH    value of pH<7, and comprising a developing substance and at least    one coupling substance, or-   c4) then applying to the treated fibres a dye of formula (1), or a    dye of formula (4), or a composition comprising a dye of formula    (1), and a composition, possessing a pH value of pH>7, and    comprising a developing substance and at least one coupling    substance, or-   c5) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising a dye of formula (1), or a    composition comprising a dye of formula (1), or-   c6) then applying to the treated fibres a composition, possessing a    pH value of pH<7, and comprising a dye of formula (1), or a    composition comprising a dye of formula (1), or in a further    embodiment of the invention-   c7) then applying to the treated fibres a dye of formula (1)    according to claim 1, or a dye of formula (4) or a composition    comprising a dye of formula (1), and a composition, possessing a pH    value of pH<7, and comprising a developing substance and at least    one coupling substance and an oxidation agent, or-   c8) then applying to the treated fibres a dye of formula (1), or a    dye of formula (4), or a composition comprising a dye of formula    (1), and a composition, possessing a pH value of pH>7, and    comprising a developing substance and at least one coupling    substance and an oxidation agent, or-   c9) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising an oxidation agent and a dye of    formula (1), or a composition comprising a dye of formula (1), or-   c10) then applying to the treated fibres a composition, possessing a    pH value of pH<7, and comprising an oxidation agent and a dye of    formula (1), or a composition comprising a dye of formula (1),-   with the proviso that least one dye of formula (1), or a composition    comprising a dye of formula (1), applied to the hair.

One further preferred embodiment method of colouring keratin-containingfibres comprises

-   a3) treating the fibres with a dye of formula (1), or with a dye of    formula (4), or with a composition comprising a dye of formula (1),    and a composition, possessing a pH value of pH>7, and comprising a    developing substance and at least one coupling substance and an    oxidation agent, or-   a4) treating the fibres with a dye of formula (1) according to claim    1, or with a dye of formula (4), or with a composition comprising a    dye of formula (1), and a composition, possessing a pH value of    pH<7, and comprising a developing substance and at least one    coupling substance and an oxidation agent, and-   b) then applying without intermediary rinsing for 5 to 30 minutes,    and-   c1) then applying to the treated fibres a composition, possessing a    pH value of pH<7, and comprising a developing substance and at least    one coupling substance, or-   c2) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising a developing substance and at least    one coupling substance, or-   c3) then applying to the treated fibres a dye of formula (1)    according to claim 1, or a dye of formula (4) or a composition    comprising a dye of formula (1), and a composition, possessing a pH    value of pH<7, and comprising a developing substance and at least    one coupling substance, or-   c4) then applying to the treated fibres a dye of formula (1), or a    dye of formula (4), or a composition comprising a dye of formula    (1), and a composition, possessing a pH value of pH>7, and    comprising a developing substance and at least one coupling    substance, or-   c5) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising a dye of formula (1), or a    composition comprising a dye of formula (1), or-   c6) then applying to the treated fibres a composition, possessing a    pH value of pH<7, and comprising a dye of formula (1), or a    composition comprising a dye of formula (1), or in a further    embodiment of the invention-   c7) then applying to the treated fibres a dye of formula (1)    according to claim 1, or a dye of formula (4) or a composition    comprising a dye of formula (1), and a composition, possessing a pH    value of pH<7, and comprising a developing substance and at least    one coupling substance and an oxidation agent, or-   c8) then applying to the treated fibres a dye of formula (1), or a    dye of formula (4), or a composition comprising a dye of formula    (1), and a composition, possessing a pH value of pH>7, and    comprising a developing substance and at least one coupling    substance and an oxidation agent, or-   c9) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising an oxidation agent and a dye of    formula (1), or a composition comprising a dye of formula (1), or-   c10) then applying to the treated fibres a composition, possessing a    pH value of pH<7, and comprising an oxidation agent and a dye of    formula (1), or a composition comprising a dye of formula (1), or-   c11) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising a developing substance and at least    one coupling substance, or-   c12) then applying to the treated fibres a composition, possessing a    pH value of pH>7, and comprising an oxidation agent and a developing    substance and at least one coupling substance, or-   with the proviso that least one dye of formula (1), or a composition    comprising a dye of formula (1), applied to the hair.

In one preferred embodiment of the invention dyes of formula (1) or (4)or further cationic dyes are mixed with the other components of thecompositions shortly before the applying to the hair.

In addition, the methods of colouring of the present invention can becarried out on hair, with preference being given to locks of hair, locksof bleached hair, bleached hair, middle blonde hair.

Further one preffered embodiment of methods of colouring of the presentinvention concerns the colouring by a comb.

The present invention relates also to compositions comprising such dyesfor colouring keratin-containing fibres.

The compounds of formulae (1) and (2) are present in the compositionsaccording to the invention preferably in an amount of from 0.001% to 5%,especially from 0.01% to 1%, based on the total dyeing composition.

The multiplicity of shades and the colour fastness of the dyes offormulae (1) and (2) used in accordance with the invention can beincreased by combination with other dyes used in the field ofhair-dyeing compositions. They can be combined very readily both withoxidation dyes and with direct dyes, it being possible for the latter tobe of cationic nature or also uncharged. Only in the case of anionicdirect dyes is a certain degree of caution required, since precipitationmay occur in the formulation under certain circumstances.

In all dyeing compositions, the joint use of a plurality of differentdyeing substances is also possible; similarly possible is the joint useof a plurality of different oxidation dye precursors from the group ofthe developer and coupler compounds, for example aromatic compoundshaving a primary or secondary amino group, nitrogen-containingheterocycles, aromatic hydroxy compounds or amino acids, as described,for example, in German Patent Application 19 717 224.5, especially page3, line 31 to page 5, line 8.

The dyes of formulae (1) and (2) according to the invention producecolour shades in the range from reddish-violet to violet, and thefastness properties are excellent. Attention is drawn to the propertythereof that allows hair that is already dark in colour still to bedistinctly altered in shade.

For colouring hair there are preferably used dyes of formula (1) inadmixture with one or more further cationic dyes, especially thosedescribed in particular on pages 11 to 27 of WO 95/01772. Especiallysuitable are dye mixtures comprising a dye of formula (1), and also theyellow dye according to Example 1 and/or the red dye according toExample 4 and/or the orange dye according to Example 46 of WO 95/1772.

In a further embodiment, for the purpose of further modification ofcolour shades the dyeing compositions according to the inventioncomprise, in addition to the dyes of formula (1) according to theinvention, customary direct dyes, for example from the group of thenitroanilines, nitrophenylenediamines, nitroaminophenols,anthraquinones, indophenols, phenazines, phenothiazines, methines or thecompounds known as Arianors, such as, for example, the compounds knownby the international names or trade names HC Yellow 2, HC Yellow 4, HCYellow 6, Basic Yellow 57, Basic Yellow 9, Disperse Orange 3, HC Red 3,HC Red SN, Basic Red 76, Basic Red 2, Basic Violet 14, Basic Blue 3,Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26,HC Blue 2, HC Blue 7, HC Blue 12, Disperse Blue 3, Basic Blue 99, HCViolet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, BasicBrown 16 und Basic Brown 17, and also picramic acid,2-amino-6-chloro-4-nitrophenol,4-amino-2-nitrodiphenylamine-2′-carboxylic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline,4-N-ethyl-1,4-bis(2′-hydroxyethylamino)-2-nitrobenzene hydrochloride and1-methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene.

Also very suitable for combination with the dyes according to theinvention are cationised nitroaniline and anthraquinone dyes, forexample those described in the following patent specifications: U.S.Pat. No. 5,298,029, especially in column 2, line 33 to column 5, line38; U.S. Pat. No. 5,360,930, especially in column 2, line 38 to column5, line 49; U.S. Pat. No. 5,169,403, especially in column 2, line 30 tocolumn 5, line 38; U.S. Pat. No. 5,256,823, especially in column 4, line23 to column 5, line 15; U.S. Pat. No. 5,135,543, especially in column4, line 24 to column 5, line 16; EP-A-818 193, especially on page 2,line 40 to page 3, line 26; U.S. Pat. No. 5,486,629, especially incolumn 2, line 34 to column 5, line 29; and EP-A-758 547, especially onpage 7, line 48 to page 8, line 19.

Also cationic azo dyes, e.g. according to GB-A-2 319 776, as well as theoxazine dyes described in DE-A-29 912 327 and mixtures thereof with theother direct dyes mentioned therein, can likewise readily be combined.

The compositions of the invention according to this embodiment containthe dyes preferably in an amount of from 0.01 to 5% by weight, based onthe total dyeing composition.

In addition, the dyeing compositions according to the invention may alsocontain naturally occurring dyes, such as, for example, henna red, hennaneutral, henna black, camomile blossom, sandalwood, black tea, Rhamnusfrangula bark, sage, campeche wood, madder root, catechu, sedre andalkanet root. Such colouring methods are described, for example, inEP-A-404 868, especially page 3, line 55 to page 4, line 9.

In respect of further customary dye components, reference is madeexpressly to the series “Dermatology”, edited by Ch. Culnan, H. Maibach,Veriag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 7, pages 248-250(direct dyes), and chapter8, pages 264-267(oxidation dyes), and to “Europäisches Inventar derKosmetikrohstoffe”, 1996, published by The European Commission,obtainable in diskette form from the Bundesverband der deutschenIndustrie und Handelsuntemehmen für Arzneimittel, Reformwaren undKörperpflegemittel e.V., Mannheim.

It is not necessary for the oxidation dye precursors optionally presentor for the dyes each to be single compounds, but rather there may bepresent in the dyeing compositions according to the invention inaddition, in lesser amounts, further components associated with thepreparation procedures for the individual dyes, provided such componentsdo not have an adverse effect on the dyeing result or do not need to beexcluded for other, for example toxicological, reasons.

The dyes of formula (1) according to the invention may also readily beused in combination with other dyes and/or adjuvants used in thecolouring of hair, for example with

-   -   oxidising agents to achieve lightened colouration, as described        in WO 97/20545, especially page 9, lines 5 to 9,    -   oxidising agents in the form of permanent-wave fixing solution,        as described in DE-A-19 713 698, especially page 4, lines 52 to        55, or EP-A-1 062 940, especially page 6, lines 41 to 47, (and        in the equivalent WO 99/40895),    -   oxidation dyeing compositions, as described in EP-A-850 636,        especially page 5, line 41 to page 7, line 52, EP-A-850 837,        especially page 6, line 50 to page 8, line 44, EP-A-850 638,        especially page 7, line 20 to page 9, line 26, and EP-A-852 135,        especially page 4, line 54 to page 6, line 53,    -   oxidation dyeing compositions with cationic couplers, as        described in WO 99/48856, especially page 9, line 16 to page 13,        line 8, and WO 99/48875, especially page 11, line 20 to page 12,        line 13,    -   oxidation dyes in the presence of oxidoreductase enzyme, as        described in WO 99/17730, especially page 4, line 11 to page 13,        line 28, and WO 99/36034, especially pages 3 to 15,    -   autooxidisable oxidation dyes, as described in WO 99/20234,        especially page 26, line 16 to page 28, line 15, or    -   nitrobenzene derivatives, as described in WO 99/20235,        especially page 26, line 7 to page 30, line 15,    -   polyols or polyethers, as described in EP-A-962 219, especially        page 27, lines 14 to 38, thickening polymers, as described in        EP-A-970 684, especially page 48, line 16 to page 51, line 4,    -   sugar-containing polymers, as described in EP-A-970 687,        especially page 28, line 17 to page 29, line 23,    -   quaternary ammonium salts, as described in WO 00/10517,        especially page 44, line 16 to page 46, line 23,    -   anionic surfactants, as described in WO 00/10518, especially        page 45, line 11 to page 48, line 3,    -   non-ionic surfactants, as described in WO 00/10519, especially        page 45, line 11 to page 50, line 12, or    -   silicones, as described in WO 00/12057, especially page 45, line        9 to page 55, line 2.

The dyeing compositions according to the invention result in intensecolourations even at physiologically tolerable temperatures of less than45° C. They are accordingly suitable especially for colouring humanhair. For use on human hair, the dyeing compositions can usually beincorporated into an aqueous cosmetic carrier. Suitable aqueous cosmeticcarriers include, for example, creams, emulsions, gels and alsosurfactant-containing foaming solutions, e.g. shampoos or otherpreparations, that are suitable for use on keratin-containing fibres.Such forms of use are described in detail in Research Disclosure42448(August 1999). If necessary, it is also possible to incorporate thedyeing compositions into anhydrous carriers, as described, for example,in U.S. Pat. No. 3,369,970, especially column 1, line 70 to column 3,line 55. The dyeing compositions according to the invention are alsoexcellently suitable for the colouring method described in DE-A-3 829870 using a colouring comb or a colouring brush.

The dyeing compositions according to the invention may furthermorecomprise any active ingredient, additive or adjuvant known for suchpreparations. The dyeing compositions in many cases comprise at leastone surfactant, there being suitable in principle anionic and alsozwitterionic, ampholytic, non-ionic and cationic surfactants. In manycases, however, it has proved advantageous to select the surfactantsfrom anionic, zwitterionic and non-ionic surfactants.

Anionic surfactants suitable for use in the preparations according tothe invention include all anionic surface-active substances that aresuitable for use on the human body. Such substances are characterised byan anionic group that imparts water solubility, for example acarboxylate, sulfate, sulfonate or phosphate group, and a lipophilicalkyl group having approximately from 10 to 22 carbon atoms. Inaddition, glycol or polyglycol ether groups, ester, ether and amidegroups and also hydroxy groups may be present in the molecule. Thefollowing are examples of suitable anionic surfactants, each in the formof sodium, potassium or ammonium salts or mono-, di- ortri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanolgroup:

-   -   linear fatty acids having from 10 to 22 carbon atoms (soaps),    -   ether carboxylic acids of formula R—O—(CH₂—CH₂—O)—_(x)—CH₂—COOH,        in which R is a linear alkyl group having from 10 to 22 carbon        atoms and x=0 or from 1 to 16,    -   acyl sarcosides having from 10 to 18 carbon atoms in the acyl        group,    -   acyl taurides having from 10 to 18 carbon atoms in the acyl        group,    -   acyl isothionates having from 10 to 18 carbon atoms in the acyl        group,    -   sulfosuccinic mono- and di-alkyl esters having from 8 to 18        carbon atoms in the alkyl group and sulfosuccinic        monoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in        the alkyl group and from 1 to 6 oxyethyl groups,    -   linear alkane sulfonates having from 12 to 18 carbon atoms,    -   linear α-olefin sulfonates having from 12 to 18 carbon atoms,    -   α-sulfo fatty acid methyl esters of fatty acids having from 12        to 18 carbon atoms,    -   alkyl sulfates and alkyl polyglycol ether sulfates of formula        R′—O(CH₂—CH₂—O)_(x)SO₃H, in which R′ is a preferably linear        alkyl group having from 10 to 18 carbon atoms and x′=0 or from 1        to 12,    -   mixtures of surface-active hydroxysulfonates according to DE-A-3        725 030, especially page 3, lines 40 to 55,    -   sulfated hydroxyalkylpolyethylene and/or        hydroxyalkylenepropylene glycol ethers according to DE-A-3 723        354, especially page 4, lines 42 to 62,    -   sulfonates of unsaturated fatty acids having from 12 to 24        carbon atoms and from 1 to 6 double bonds according to DE-A-3        926 344, especially page 2, lines 36 to 54,    -   esters of tartaric acid and citric acid with alcohols which are        addition products of approximately from 2 to 15 molecules of        ethylene oxide and/or propylene oxide with fatty alcohols having        from 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ethersulfates and ether carboxylic acids having from 10 to 18 carbon atoms inthe alkyl group and up to 12 glycol ether groups in the molecule, andalso especially salts of saturated and especially unsaturatedC₈-C₂₂carboxylic acids, such as oleic acid, stearic acid, isostearicacid and palmitic acid.

Surface-active compounds that carry at least one quaternary ammoniumgroup and at least one —COO⁽⁻⁾or —SO⁽⁻⁾ group in the molecule are termedzwitterionic surfactants. Zwitterionic surfactants that are especiallysuitable are the so-called betaines, such as theN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyl-dimethylammonium glycinate, and2-alkyl-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocamidopropyl betaine.

Ampholytic surfactants are to be understood as meaning surface-activecompounds that, in addition to a C₈-C₁₈-alkyl or -acyl group, contain atleast one free amino group and at least one —COOH or —SO₃H group in themolecule and are capable of forming internal salts. Examples of suitableampholytic surfactants include N-alkylglycines, N-alkylproplonic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given are Ncocoalkyl-aminopropionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈acylsarcosine.

Non-ionic surfactants contain as the hydrophilic group, for example, apolyol group, a polyalkylene glycol ether group or a combination ofpolyol and polyglycol ether groups.

Such compounds are, for example:

-   -   addition products of from 2 to 30 mol of ethylene oxide and/or        from 0 to 5 mol of propylene oxide with linear fatty alcohols        having from 8 to 22 carbon atoms, with fatty acids having from        12 to 22 carbon atoms and with alkylphenols having from 8 to 15        carbon atoms in the alkyl group,    -   C₁₂-C₂₂ fatty add mono- and di-esters of addition products of        from 1 to 30 mol of ethylene oxide with glycerol,    -   C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated        analogues thereof, addition products of from 5 to 60 mol of        ethylene oxide with castor oil and hydrogenated castor oil,    -   addition products of ethylene oxide with sorbitan fatty acid        esters,    -   addition products of ethylene oxide with fatty acid        alkanolamides.

Examples of cationic surfactants that can be used in the hair-treatmentcompositions according to the invention are especially quaternaryammonium compounds. Preference is given to ammonium halides, such asalkyltrimethylammonium chlorides, dialkyldimethyl-ammonium chlorides andtrialkylmethylammonium chlorides, for example cetyltrimethyl-ammoniumchloride, stearyltrimethylammonium chloride, distearyldlmethylammoniumchloride, lauryidimethylammonium chloride, lauryldimethylbenzylammoniumchloride and tricetylmethylammonium chloride. Further cationicsurfactants that can be used in accordance with the invention arequaternised protein hydrolysates.

Also suitable in accordance with the invention are cationic siliconeoils, such as, for example, the commercially available productsQ2-7224(manufacturer: Dow Corning; a stabilisedtrimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising ahydroxylamino-modified silicone, which is also referred to asamodimethicone), SM-2059(manufacturer General Electric),SLM-55067(manufacturer Wacker) and also Abil®-Quat 3270 and 3272(manufacturer Th. Goldschmidt; diquaternary polydimethylsiloxanes,quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines, such as thestearylamidopropyl-dimethylamine obtainable under the name Tego Amid®18, are distinguished not only by a good conditioning action but alsoespecially by their good biodegradability.

Quaternary ester compounds, so-called “esterquats”, such as the methylhydroxyalkyl-dialkoyloxyalkylammonium methosulfates marketed under thetrade mark Stepantex®, are also very readily biodegradable.

An example of a quaternary sugar derivative that can be used as cationicsurfactant is the commercial product Glucquat®100, according to CTFAnomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimoniumchloride”.

The alkyl-group-containing compounds used as surfactants may be singlesubstances, but the use of natural raw materials of vegetable or animalorigin is generally preferred in the preparation of such substances,with the result that the substance mixtures obtained have differentalkyl chain lengths according to the particular starting material used.

The surfactants that are addition products of ethylene and/or propyleneoxide with fatty alcohols or derivatives of such addition products mayeither be products having a “normal” homologue distribution or productshaving a restricted homologue distribution. “Normal” homologuedistribution is to be understood as meaning mixtures of homologuesobtained in the reaction of fatty alcohol and alkylene oxide usingalkali metals, alkali metal hydroxides or alkali metal alcoholates ascatalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkali metal salts of ethercarboxylic acids, alkali metal oxides, hydroxides or alcoholates areused as catalysts. The use of products having restricted homologuedistribution may be preferred.

Examples of further active ingredients, adjuvants and additives are asfollows:

-   -   non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate        copopylmers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl        acetate copolymers and polysiloxanes,    -   cationic polymers, such as quaternised cellulose ethers,        polysiloxanes having quaternary groups, dimethyldiallylammonium        chloride polymers, copolymers of dimethyldiallylammonium        chloride and acrylic acid, as available commercially under the        name Merquat® 280 and the use of which in hair colouring is        described, for example, in DE-A4 421 031, especially page 2,        lines 20 to 49, or EP-A-953 334, especially page 27, line 17 to        page 30, line 11, acrylamide/dimethyldiallylammonium chloride        copolymers, diethyl-sulfate-quaternised dimethylaminoethyl        methacrylate/vinylpyrrolidone copolymers,        vinylpyrrolidone/imidazolinium methochloride copolymers,    -   quaternised polyvinyl alcohol,    -   zwitterionic and amphoteric polymers, such as, for example,        acrylamidopropyl-trimethylammonium chloride/acrylate copolymers        and octylacrylamide/methyl methacrylate/tert-butylaminoethyl        methacrylate/2-hydroxypropyl methacrylate copolymers,    -   anionic polymers, such as, for example, polyacrylic acids,        crosslinked polyacrylic acids, vinyl acetate/crotonic acid        copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl        acetate/butyl maleate/isobornyl acrylate copolymers, methyl        vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl        acrylate/N-tert-butyl acrylamide terpolymers,    -   thickeners, such as agar, guar gum, alginates, xanthan gum, gum        arabic, karaya gum, locust bean flour, linseed gums, dextrans,        cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl        cellulose and carboxymethyl cellulose, starch fractions and        derivatives, such amylose, amylopectin and dextrins, clays, e.g.        bentonite or fully synthetic hydrocolloids such as, for example,        polyvinyl alcohol,    -   structuring agents, such as glucose and maleic acid,    -   hair-conditioning compounds, such as phospholipids, for example        soya lecithin, egg lecithin, and cephalins, silicone oils, and        also conditioning compounds, for example such as those described        in DE-A-19 729 080, especially page 2, lines 20 to 49, EP-A-834        303, especially page 2, line 18 to page 3, line 2, or EP-A-312        343, especially page 2, line 59 to page 3, line 11,    -   protein hydrolysates, especially elastin, collagen, keratin,        milk protein, soya protein and wheat protein hydrolysates,        condensation products thereof with fatty acids and also        quaternised protein hydrolysates,    -   perfume oils, dimethyl isosorbitol and cyclodextrins,    -   solubilisers, such as ethanol, isopropanol, ethylene glycol,        propylene glycol, glycerol and diethylene glycol,    -   anti-dandruff active ingredients, such as piroctones, olamines        and zinc Omadine,    -   further substances for adjusting the pH value,    -   active ingredients such as panthenol, pantothenic acid,        allantoin, pyrrolidonecarboxylic acids and salts thereof, plant        extracts and vitamins,    -   cholesterol,    -   light stabilisers and UV absorbers, as described, for example,        in EP-A419 422, especially page 4, lines 34 to 37,    -   consistency regulators, such as sugar esters, polyol esters or        polyol alkyl ethers,    -   fats and waxes, such as spermaceti, beeswax, montan wax,        paraffins, fatty alcohols and fatty acid esters,    -   fatty alkanolamides,    -   polyethylene glycols and polypropylene glycols having a        molecular weight of from 150 to 50 000, for example such as        those described in EP-A-801 942, especially page 3, lines 44 to        55,    -   complexing agents, such as EDTA, NTA and phosphonic acids,    -   swelling and penetration substances, such as polyols and polyol        ethers, as listed extensively, for example, in EP-A-962 219,        especially page 27, lines 18 to 38, for example glycerol,        propylene glycol, propylene glycol monoethyl ether, butyl        glycol, benzyl alcohol, carbonates, hydrogen carbonates,        guanidines, ureas and also primary, secondary and tertiary        phosphates, imidazoles, tannins, pyrrole,    -   opacifiers, such as latex,    -   pearlising agents, such as ethylene glycol mono- and        di-stearate,    -   propellants, such as propane-butane mixtures, N₂O, dimethyl        ether, CO₂ and air, and also    -   antioxidants.

The constituents of the aqueous carrier are used in the preparation ofthe dyeing compositions according to the invention in the amountscustomary for that purpose; for example emulsifiers are used inconcentrations of from 0.5 to 30% by weight and thickeners inconcentrations of from 0.1 to 25% by weight of the total dyeingcomposition.

The pH value of the ready-to-use dyeing preparations are usually from 2to 11, preferably from 5 to 10.

To colour keratin-containing fibres, especially to colour human hair,the dyeing compositions are usually applied to the hair in an amount offrom 50 to 100 g in the form of the aqueous cosmetic carrier, left therefor approximately 30 minutes and then rinsed off or washed off with acommercially available hair shampoo.

The dyes used according to the invention and the optionally usedoxidation dye precursors may be applied to the keratin-containing fibreseither simultaneously or in succession, the order in which they areapplied being unimportant.

The dyes used according to the invention and the optionally usedoxidation dye precursors of the compositions according to the inventionmay be stored separately or together, either in a liquid to paste-likepreparation (aqueous or non-aqueous) or in the form of a dry powder.When the components are stored together in a liquid preparation, thepreparation should be substantially anhydrous in order to reducereaction of the components. When they are stored separately, thereactive components are intimately mixed with one another onlyimmediately before use. In the case of dry storage, before use a definedamount of hot (from 50 to 80° C.) water is usually added and ahomogeneous mixture prepared.

The following Examples serve to illustrate the invention withoutlimiting the invention thereto. Unless specified otherwise, parts andpercentages relate to weight.

EXAMPLE 1

16 g of the compound of formula

are introduced into 65 g of acetic anhydride and stirring is carried outfor 2 hours at a bath temperature of approximately 75° C., after whichtime all starting material has disappeared. After cooling, filtration iscarried out and then washing with acetic anhydride. In order to removethe acetic anhydride, the filter cake is suspended in 200 ml ofisopropanol, and the suspension is stirred for 2 hours and filteredagain and washed with isopropanol, 17.8 g of the compound of formula

is obtained in very pure form. In aqueous solution, the compound dyesbleached yak hair a brilliant red-tinged violet.

The acetylation can also be carried out in solvents, for example inwater 110 g of the above-described starting compound are suspended in300 ml of water and, at a temperature of approximately 70° C., a totalof 61.4 g of acetic anhydride (=100% excess) are added over a period ofone hour. The reaction mixture is cooled with stirring, then filteredand washed with water. After drying, 122.5 g of the acetylated compoundare obtained in which only traces of the starting material are stillpresent.

EXAMPLE 2

With stirring, 15 g of the compound of formula

are slowly added to 30 g of formic add (98%) and heating is carried outfor 3 hours at 65° C. 100 ml of isopropanol are added dropwise to thehot solution, which is then stirred until cold. Filtration followed bythorough washing with isopropanol are carried out. The moist filter cakeis first stirred into 65 ml of methanol barely at reflux, and thenfiltration at 45° C. followed by washing with methanol are carried out.The filter cake is then dissolved hot in 1.5 liters of methanol, thesolution is clarified and the mother liquor is concentrated toapproximately 85 g using a rotary evaporator, in the course of whichthere is already partial precipitation of the dye. After cooling suctionfiltration is carried out, followed by washing with a small amount ofmethanol and drying. Approximately 9 g of the dye of formula

are obtained. In aqueous solution, the dye colours bleached yak hair abrilliant red-tinged violet.

EXAMPLE 3

10.3 g of the compound of formula

are dissolved in 33 ml of 1 N hydrochloric acid in an ice-cooledapparatus. 30 g of ice are added to the reaction solution and then, overa period of half an hour, 2.4 g of potassium cyanate are added inportions. Towards the end a honey-like residue forms, which maysometimes block the stirrer. After standing for from 1 to 2 hours in anice bath, the residue nas turned into a brittle mass that can readily becrushed using a glass rod. The suspension, readily stirrable again,still contains significant amounts of starting material and therefore afurther 9 ml of HCl (1N) and 1.2 g of KOCN are added. The ice bath isthen removed and filtration at room temperature is carried out. Theresidue is suspended in water again and stirred at 75° C. for 2 hours.After cooling, filtration and washing with water are carried out.

For purification, the residue is dissolved hot in 12 liters of methanoland the solution is clarified by way of a preheated pressurised suctionfilter. The filtrate is concentrated to approximately 2 liters using arotary evaporator, the dye precipitating in pure form. Followingcooling, filtration and washing with methanol, 24 g of the dye offormula

are obtained. In aqueous solution, the dye colours bleached yak hair abrilliant violet, the shade of which is slightly less red-tinged thanthat of the formyl-substituted dye of Example 2.

EXAMPLE 4

13 g of p-anisidine are dissolved at approximately 50° C. in 45 g ofdimethyl-formamide in a suitable stirring apparatus. Then, withstirring, 26.7 g of the compound of formula

are added in portions and the mixture is stirred for 80 hours at a bathtemperature of 90° C. under nitrogen. While still hot, the reactionmixture is diluted with a further 50 g of dimethyl-formamide, allowed tocool slightly and filtered at approximately 40° C. The crystallinefilter cake is washed with a further 50 g of DMF in portions, andfinally thoroughly suction-filtered dry.

In order to remove small amounts of starting material that are stillpresent, the filter cake is suspended in 80 g of water and stirred for 2hours at a temperature of from 70 to 75° C. After cooling with stirring,filtration is carried out, followed by washing with a total of 50 g ofwater, in portions, and drying, 22 g of the dye of formula

are obtained. In aqueous solution, the dye colours bleached yak hair abrilliant red-tinged violet.

EXAMPLE 5

A 10% solution of a non-ionic surfactant (Plantaren® 2000 [Henkel]) isadjusted to pH 9.5 using citric acid. 0.06% of the dye from Example 1are dissolved therein. A 1 g strand of undamaged human hair (“Italianwhite virgin”, Imhair Ltd) is treated for 20 minutes at room temperaturewith 2 g of the dye solution and then rinsed and shampooed. A veryattractive violet colouration is obtained, which even after washingeight times can still be seen clearly. The fastness to tight of thecolouration is excellent.

EXAMPLE 6

A 10% solution of a non-ionic surfactant (Plantaren® 2000 [Henkel]) isadjusted to pH 5.5 using citric acid. The following dyes are dissolvedin 100 g of that solution: 0.20 g of the yellow dye according to Example1 in WO 95/01772 0.05 g of the dye according to the invention fromExample 4 of the present Application.

A 1 g strand of undamaged human hair (“Italian white virgin”, ImhairLtd) is treated for 20 minutes at room temperature with 2 g of the abovedye solution and then rinsed and shampooed. A very attractive coppercolouration having excellent fastness to washing, rubbing and light isobtained.

EXAMPLE 7

A 10% solution of a non-ionic surfactant (Plantaren® 2000 [Henkel]) isadjusted to pH 5.5 using citric acid. The following dyes are dissolvedin 100 g of that solution:

-   0.25 g of the yellow dye according to Example 1 in WO 95/01772-   0.08 g of the orange dye according to Example 46 in WO 95/01772-   0.06 g of the dye according to the invention from Example 2 of the    present Application.-   0.11 g of the blue dye according to Example 6 in WO 95/01772.

A strand of bleached human hair is treated for 20 minutes at roomtemperature with double the amount thereof of the above dyeing solution,and is then rinsed and shampooed once. A black colouration having goodfastness to washing and rubbing is obtained.

EXAMPLE 8

The following cationic emulsion base is prepared:

-   3.8 g of behenic trimonium chloride (Genamin KDM-P [Hoechst])-   4.0 g of cetyl alcohol (Lanette 16 [Henkel])-   0.5 g of phenoxyethanol (Uniphen P23 [Induchem])-   0.1 g of perfume (PÖ Cinque 226482 [drom])-   water ad 100

0.06 g of the dye according to Example 4 of the present Application isdissolved in the above base and the pH is adjusted to 6.5 usingmonoethanolamine. A 1 g strand of undamaged medium-brown human hair(virgin medium-brown hair, Imhair Ltd.) is treated for 20 minutes atroom temperature with 2 g of the above dyeing emulsion, and is thenrinsed and shampooed once. The hair acquires a very attractive intenseaubergine shade having excellent fastness properties.

EXAMPLE 9

A 10% solution of a nonionic surfactant (Plantaren® 2000 [Henkel]) isadjusted to pH 5.5 using citric acid. The following dyes are dissolvedin 100 g of that solution:

-   0.06 g of the yellow dye according to Example 1 in WO 95/01772-   0.09 g of the orange dye according to Example 46 in WO 95/01772-   0.03 g of the dye according to the invention from Example 4 of the    present Application-   0.07 g of the blue dye according to Example 6 in WO 95/01772.

A strand of bleached human hair and a strand of undamaged white humanhair are each treated for 20 minutes at room temperature with double theamount thereof of the above dyeing solution, and are then rinsed andshampooed once. In both cases the result is a dark-brown colourationwith a distinct, very attractive violet tinge.

EXAMPLE 10

The following dyes are dissolved in 100 g of a solution of a non-ionicsurfactant as described in Example 5(pH 9.5):

-   0.14 g of Basic Red 76(Arianor® Madder Red),-   0.14 g of the dye according to the invention from Example 4,-   0.28 g of Basic Blue 99(Arianor® Steel Blue),-   0.28 g of HC Yellow 2 and-   0.14 g of the yellow dye according to Example 1 in WO 95/01772.

A strand of white, undamaged hair is treated for 20 minutes at roomtemperature with the above solution. The result is a light-browncolouration with an attractive copper tinge.

EXAMPLE 11

The procedure is as in Example 10, except that the dyes specified arereplaced by

-   0.4 g of the red dye according to Example 3 in WO 95/01772 and-   0.1 g of the dye according to the invention from Example 4.

The result on the white hair is a very attractive, intensely ruby-redcolouration having excellent fastness properties.

EXAMPLE 12

Compositions (A) below, in accordance with the invention, are prepared(contents in grams):

Composition 1(A) 2(A) 3(A) 4(A) 5(A) 6(A) 7(A) 8(A)Para-toluylenediamine 0.25 — — — — — — 0.70 2,4-Diamino-1-(-(β- — — — —— — — 0.35 hydroxyethyloxy)benzene Para-phenylenediamine — 0.20 — 0.301.00 0.70 0.70 — Para-aminophenol 0.30 0.50 0.15 — — — — —5-N-(β-Hydroxyethyl) 0.50 0.80 0.17 — — — — — amino-2-methylphenol1,3-Dihydroxybenzene — — — — 0.50 0.50 — — 5-Amino-methylphenol — — —0.30 — — — — Cationic dye of example 4 0.15 0.20 0.05 0.10 0.25 0.100.50 0.40 Common dye support(*) (*) (*) (*) (*) (*) (*) (*) (*) Water qs100 100 100 100 100 100 100 100 (*) Common dye support: Oleyl alcoholpolyglycerolated with 4.0 g 2 mol of glycerol Oleyl alcoholpolyglycerolated with 5.69 g A.M. 4 mol of glycerol, containing 78%active material (A.M.) Olaic acid 3.0 g Oleylamine containing 2 mol ofethylene oxide, sold under the trade name Ethomeen O12 by the companyAkzo Diethylaminopropyllaurylaminosuccinamate, 3.0 g A.M. sodium salt,containing 55% A.M. Oleyl alcohol 5.0 g Oleic acid diethanolaminde 12.0g Propylene glycol 3.5 g Ethyl alcohol 7.0 g Diproplene glycol 0.5 gPropylene glycol monomethyl ether 9.0 g Sodium metabisulphite as anaqueous solution 0.455 g A.M. containing 35% A.M. Ammonium acetate 0.8 gAntioxidant, sequestering agent qs Fragrance, preserving agent qsAqueous ammonia containing 20% NH₃ 10.0 g

Compositions 9(A)^(I) to 32(A)^(I) are identical to composition 2(A),and compositions 9(A)^(II) to 32(A)^(II) are identical to composition4(A), and compositions 9(A)^(III) to 32(A)^(III) are identical tocomposition 5(A), and compositions 9(A)^(IV) to 32(A)^(IV) are identicalto composition 6(A), and compositions 9(A)^(V) to 32(A)^(V) areidentical to composition 7(A), with the proviso thatpara-phenylenediamine is replaced by a compound C as given below intable 1.

Compositions 34(A)^(I) to 57(A)^(I) are identical to composition 8(A),with the proviso that 2,4-diamino-1-(-β-hydroxyethyloxy)benzene isreplaced by a compound C as given below in table 1.

Compositions 59(A)^(I) to 81(A)^(I) are identical to composition 1(A),and compositions 59(A)^(I′I) to (A)^(I′I) identical to composition 8(A),with the proviso that para-toluylenediamine is replaced by a compound Cas given below in table 1.

TABLE 1 Compositions Compound C 9(A)^(I-V), 34(A)^(I), 59(A)^(I-II)2-chloro-para-phenylendiamine 10(A)^(I-V), 35(A)^(I), 60(A)^(I-II)2,3-dimethyl-para-phenylenediamine 11(A)^(I-V), 36(A)^(I), 61(A)^(I-II)2,6-dimethyl-para-phenylenediamine 12(A)^(I-V), 37(A)^(I), 62(A)^(I-II)2,6-diethyl-para-phenylenediamine 13(A)^(I-V), 38(A)^(I), 63(A)^(I-II)2,5-dimethyl-para-phenylenediamine 14(A)^(I-V), 39(A)^(I), 64(A)^(I-II)N,N-dimethyl-para-phenylenediamine 15(A)^(I-V), 40(A)^(I), 65(A)^(I-II)N,N-diethyl-para-phenylenediamine 16(A)^(I-V), 41(A)^(I), 66(A)^(I-II)N,N-dipropyl-para-phenylenediamine 17(A)^(I-V), 42(A)^(I), 66(A)^(I-II)4-amino-N,N-diethyl-3-methylaniline 18(A)^(I-V), 43(A)^(I), 66(A)^(I-II)N,N-bis(.beta.-hydroxyethyl)-para- phenylenediamine 19(A)^(I-V),44(A)^(I), 67(A)^(I-II) 4-amino-N,N-bis(.beta.-hydroxyethyl-3-methylaniline 20(A)^(I-V), 45(A)^(I), 68(A)^(I-II)4-amino-3-chloro-N,N-bis(.beta.- hydroxyethyl)aniline 21(A)^(I-V),46(A)^(I), 69(A)^(I-II) 2-.beta.-hydroxyethyl-para- phenylenediamine22(A)^(I-V), 47(A)^(I), 70(A)^(I-II) 2-fluoro-para-phenylenediamine23(A)^(I-V), 48(A)^(I), 71(A)^(I-II) 2-isopropyl-para-phenylenediamine24(A)^(I-V), 49(A)^(I), 72(A)^(I-II) N-(.beta.-hydroxypropyl)-para-phenylenediamine 25(A)^(I-V), 50(A)^(I), 74(A)^(I-II)2-hydroxymethyl-para-phenylenediamine 26(A)^(I-V), 51(A)^(I),75(A)^(I-II) N,N-dimethyl-3-methyl-para- phenylenediamine 27(A)^(I-V),52(A)^(I), 76(A)^(I-II) N,N-(ethyl-.beta.-hydroxyethyl)-para-phenylenediamine 28(A)^(I-V), 53(A)^(I), 77(A)^(I-II)N-(.beta.,.gamma.-dihydroxypropyl)-para- phenylenediamine 29(A)^(I-V),54(A)^(I), 78(A)^(I-II) N-(4′-aminophenyl)-para-phenylenediamine30(A)^(I-V), 55(A)^(I), 79(A)^(I-II) N-phenyl-para-phenylenediamine31(A)^(I-V), 80(A)^(I-II) 2-.beta.-hydroxyethyloxy-para-phenylenediamine 32(A)^(I-V), 57(A)^(I), 81(A)^(I-II)2-.beta.-acetylaminoethyloxy-para- phenylenediamine

Compositions 100(A)^(I) to 107(A)^(I) are identical to composition 1(A),and compositions 100(A)^(II) to 107(A)^(II) are identical to composition8(A), with the proviso that para-toluylenediamine is replaced by acompound C as given below in table 2.

Compositions 108(A)^(I) to 114(A)^(I) are identical to composition 1(A),and compositions 108(A)^(II) to 114(A)^(II) are identical to composition8(A), with the proviso that para-phenylenediamine is replaced by acompound C as given below in table 2.

TABLE 2 Compositions Compound C 100(A)^(I-II), 108(A)^(I-II)N,N′bis(.beta.-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol 101(A)^(I-II), 109(A)^(I-II)N-N′-bis(.beta.-hydroxyethyl)-N,N′-bis(4′- aminophenyl)ethylenediamine103(A)^(I-II), 110(A)^(I-II)N,N′-bis(4-aminophenyl)tetramethylenediamine 104(A)^(II-II),111(A)^(I-II) N,N′-bis(.beta.-hydroxyethyl)-N 105(A)^(I-II),112(A)^(I-II) N′-bis(4-aminophenyl)tetramethylenediamine 106(A)^(I-II),113(A)^(I-II) N,N′-bis(4-methylaminophenyl) tetramethylenediamine107(A)^(I-II), 114(A)^(I-II) N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine

Compositions 200(A)^(I) to 210(A)^(I) are identical to composition 1(A),and compositions 200(A)^(II) to 210(A)^(II) are identical to composition2(A), and compositions 200(A)^(III) to 210(A)^(III) are identical tocomposition 3(A), with the proviso that para-aminophenol is replaced bya compound C as given below in table 3.

TABLE 3 Compositions Compound C 200(A)^(I-III) 4-amino-3-methylphenol203(A)^(I-III) 4-amino-3-flourophenol 204(A)^(I-III)4-amino-3-hydroxymethylphenol 205(A)^(I-III) 4-amino-2-methylphenol206(A)^(I-III) 4-amino-2-hydroxymethylphenol 207(A)^(I-III)4-amino-2-methoxymethyl-phenol 208(A)^(I-III)4-amino-2-aminomethylphenol 209(A)^(I-III)4-amino-2-(.beta.-hydroxyethylaminoethyl)phenol 210(A)^(I-III)4-amino-2-flouro-phenol

Compositions 300(A)^(I) to 304(A)^(I) are identical to composition 1(A),and compositions 300(A)^(II) to 304(A)^(II) are identical to composition2(A), and compositions 300(A)^(III) to 304(A)^(III) are identical tocomposition 3(A), with the proviso that para-aminophenol is replaced bya compound C as given below in table 3.

TABLE 3 Compositions Compound C 300(A)^(I-III) 2-amino-phenol301(A)^(I-III) 2-amino-5-methylphenol 303(A)^(I-III)2-amino-6-methylphenol 304(A)^(I-III) 5-acetamido-2-aminophenol

Compositions 400(A)^(I) to 404(A)^(I) are identical to composition (A),and compositions 400(A)^(II) to 404(A)^(II) are identical to composition4(A), and compositions 400(A)^(III) to 404(A)^(III) are identical tocomposition 5(A), and compositions 400(A)^(IV) to 404(A)^(IV) areidentical to composition 6(A), and compositions 400(A)^(V) to 404(A)^(V)are identical to composition 7(A), as given above in example 2 with theproviso that para-phenylenediamine is replaced by a compound C as givenbelow in table 4.

Compositions 405(A)^(I) to 409(A)^(I) are identical to composition 8(A),with the proviso that 2,4-diamino-1-(-(β-hydroxyethyloxy)benzene isreplaced by a compound C as given below in table 4.

Compositions 410(A)^(I) to 414(A)^(I) are identical to composition 1(A),and compositions 410(A)^(I′) to 414(A)^(I′) identical to composition8(A) as given above in example 2 with the proviso thatpara-toluylenediamine is replaced by a compound C as given below intable 4.

TABLE 4 Compositions Compound C 400(A)^(I-V), 405(A)^(I), 410(A)^(I-II)2,4,5,6-tetraaminopyrimidine 401(A)^(I-V), 406(A)^(I), 411(A)^(I-II)4-hydroxy-2,5,6-triaminopyrimidine 402(A)^(I-V), 407(A)^(I),412(A)^(I-II) 4,5-diamino-1-methylpyrazole 403(A)^(I-V), 408(A)^(I),413(A)^(I-II) 3,4-diaminopyrazole 404(A)^(I-V), 409(A)^(I),414(A)^(I-II) 4,5-diamino-1-(4′-chlorobenzyl)pyrazole

Compositions 500(A)^(I) to 521(A)^(I) are identical to composition 4(A),9(A)^(II) to 32(A)^(II) and 400(A)^(II) to 404(A)^(II) with the provisothat 5-amino-2-methylphenol is replaced by a compound C as given belowin table 5.

TABLE 5 Com- positions Compound C 500(A)^(I) 5-amino-2-methoxyphenol501(A)^(I) 5-amino-2-(.beta.-hydroxyethyloxy)phenol 502(A)^(I)5-amino-2-methylphenol 503(A)^(I)5-N-(.beta.-hydroxyethyl)amino-2-methylphenol 504(A)^(I)5-N-(.beta.-hydroxyethyl)amino-4-methoxy-2-methylphenol 505(A)^(I)5-amino-4-methoxy-2-methlyphenol 506(A)^(I)5-amino-4-chloro-2-methylphenol 507(A)^(I) 5-amino-2,4-dimethoxy-phenol508(A)^(I) 5-(.gamma.-hydroxypropylamino)-2-methylphenol 509(A)^(I)meta-phenylenediamine 510(A)^(I) 3,5-diamino-1-ethyl-2-methoxybenzene511(A)^(I) 3,5-diamino-2-methoxy-1-methylbenzene 512(A)^(I)2,4-diamino-1-ethoxybenzene 513(A)^(I)1,3-bis(2,4-diaminophenoxy)propane 514(A)^(I)bis(2,4-diaminophenoxy)methane 515(A)^(I)1-(.beta.-aminoethyloxy)-2,4-diaminobenzene 516(A)^(I)2-amino-1-(.beta.-hydroxyethyloxy)-4-methylaminobenzene 517(A)^(I)2,4-diamino-1-ethoxy-5-methylbenzene 518(A)^(I)2,4-diamino-5-(.beta.-hydroxyethyloxy)-1-methylbenzene 519(A)^(I)2,4-diamino-1-(.beta.,.gamma.-dihydroxypropyloxy)benzene 520(A)^(I)2,4-diamino-1-(.beta.-hydroxyethyloxy)benzene 521(A)^(I)2-amino-N-(.beta.-hydroxyethyl)amino-1-methoxybenzene

Compositions 800(A)^(I) to 615(A)^(I) are identical to composition1-8(A), 9(A)^(I-V) to 32(A)^(I-V), 34(A)^(I) to 57(A)^(I), 59(A)^(I-II)to 81(A)^(I-II), 100(A)^(I-II) to 107(A)^(I-II) 108(A)^(I-II) to114(A)^(I-II), 200(A)^(I-III) to 210(A)^(I-II), 300(A)^(I-III) to304(A)^(I-III), 400(A)^(I-V) to 404(A)^(I-V), 405(A)^(I) to 409(A)^(I),410(A)^(I) to 414(A)^(I-II) and 500(A)^(I) to 521(A)^(I) with theproviso that the common dye support (*) is replaced by a the common dyesupport (**) which is identical to the common dye support (*) with theproviso that “aqueous ammonia containing 20% NH₃”. is replaced by abasifying agent D as given below in table 6.

TABLE 6 common dye support (**) basifying agent D 600(A)^(I) pottassiumcarbonate 601(A)^(I) sodium carbonate 602(A)^(I) triethanolamine603(A)^(I) diethanolamine 604(A)^(I) monoethanolamine 605(A)^(I) sodiumhydroxide 606(A)^(I) potassium hydroxide 607(A)^(I)N,N-dimethyl-N′-ethylenediamine 608(A)^(I) 4-(Ethylamino)-b-butylamine609(A)^(I) N-(n-Propyl)-1,3-propanediamine 610(A)^(I)N,N-diethylenediamine 611(A)^(I) N,N,N′,N′-Tetramethylethylenediamine612(A)^(I) N,N-dimethylhydrazine 613(A)^(I) 2-n-butylaminomethylamine614(A)^(I) 1,6-diaminohexane 615(A)^(I) 2-amino-2-methyl-1-propanol

EXAMPLE 13

Compositions B (1(B), 2(B) and 3(B)) below, in accordance with theinvention, are prepared (contents in grams):

1(B) 2(B) 3(B) 1,4-Diaminobenzene 0.40 — — 5-Amino-2-methylphenol 0.45 —— Para-toluylenediamine sulphats — 0.50 0.35 Common dye support (*) as(*) (*) (*) described above in example 12 Demineralized water qs 100 100100 Cationic dye of example 4 4 4 4 Quaternary polyammonia sold 10 10 10under trade name CELQUAT SC- 240 by the company National Starch Sawdustqs 100 100 100

Compositions 4(B)^(I) to 29(B)^(I) are identical to composition 2(B),and compositions 4(B)^(II) to 29 (B)^(II) are identical to composition3(B), with the proviso that para-toluylenediamine sulphate is replacedby a compound E as given below in table 1.

Compositions 30(B)^(I) to 56(B)^(I) are identical to composition 1(B)with the proviso that 1,4-diaminobenzene is replaced by a compound E asgiven below in table 1.

TABLE 1 Compositions Compound E 4(B)^(I-II), 30(B)^(I)2-chloro-para-phenylendiamine 5(B)^(I-II), 31(B)^(I)2,3-dimethyl-para-phenylenediamine 6(B)^(I-II), 32(B)^(I)2,6-dimethyl-para-phenylenediamine 7(B)^(I-II), 33(B)^(I)2,6-diethyl-para-phenylenediamine 8(B)^(I-II), 34(B)^(I)2,5-dimethyl-para-phenylenediamine 9(B)^(I-II), 35(B)^(I)N,N-dimethyl-para-phenylenediamine 10(B)^(I-II), 37(B)^(I)N,N-diethyl-para-phenylenediamine 11(B)^(I-II), 38(B)^(I)N,N-dipropyl-para-phenylenediamine 12(B)^(I-II), 39(B)^(I)4-amino-N,N-diethyl-3-methylaniline 13(B)^(I-II), 40(B)^(I)N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine 14(B)^(I-II),41(B)^(I) 4-amino-N,N-bis(.beta.-hydroxyethyl)-3-methylaniline15(B)^(I-II), 42(B)^(I)4-amino-3-chloro-N,N-bis(.beta.-hydroxyethyl)aniline 16(B)^(I-II),43(B)^(I) 2-.beta.-hydroxyethyl-para-phenylenediamine 17(B)^(I-II),44(B)^(I) 2-fluoro-para-phenylenediamine 18(B)^(I-II), 45(B)^(I)2-isopropyl-para-phenylenediamine 19(B)^(I-II), 46(B)^(I)N-(.beta.-hydroxypropyl)-para-phenylenediamine 20(B)^(I-II), 47(B)^(I)2-hydroxymethyl-para-phenylenediamine 21(B)^(I-II), 48(B)^(I)N,N-dimethyl-3-methyl-para-phenylenediamine 22(B)^(I-II), 49(B)^(I)N,N-(ethyl-.beta.-hydroxyethyl)-para- phenylenediamine 23(B)^(I-II),50(B)^(I) N-(.beta.,.gamma.-dihydroxypropyl)-para- phenylenediamine24(B)^(I-II), 51(B)^(I) N-(4′-aminophenyl)-para-phenylenediamine25(B)^(I-II), 52(B)^(I) N-phenyl-para-phenylenediamine 26(B)^(I-II),53(B)^(I) 2-.beta.-hydroxyethyloxy-para-phenylenediamine 27(B)^(I-II),54(B)^(I) 2-.beta.-acetylaminoethyloxy-para-phenylenediamine28(B)^(I-II), 55(B)^(I) N-(.beta.-methoxyethyl)-para-phenylenediamine29(B)^(I-II), 56(B)^(I) Para-toluylenediamine

Compositions 100(B)^(I) to 109(B)^(I) are identical to composition 1(B),30(B)^(I) to 56(B)^(I), with the proviso that 5-amino-2-methylphenol isreplaced by a compound E as given below in table 2.

TABLE 2 Compositions Compound E 100(B)^(I) 5-amino-2-methoxyphenol101(B)^(I) 5-amino-2-(.beta.-hydroxyethyloxy)phenol 102(B)^(I)5-amino-2-methylphenol 103(B)^(I)5-N-(.beta.-hydroxyethyl)amino-2-methylphenol 104(B)^(I)5-N-(.beta.-hydroxyethyl)amino-4-methoxy-2- methylphenol 105(B)^(I)5-amino-4-methoxy-2-methylphenol 106(B)^(I)5-amino-4-chloro-2-methylphenol 107(B)^(I) 5-amino-2,4-dimethoxy-phenol108(B)^(I) 5-(.gamma.-hydroxypropylamino)-2-methylphenol 109(B)^(I)meta-phenylenediamine

One part by weight of composition B was mixed, at the time of use, with0.1 part by weight of composition (B′) and with one part by weight of acomposition (F) comprising a 20-volumes hydrogen peroxide solution (6%by weight).

The resulting composition was applied for 30 minutes to locks of naturalgrey hair containing 90% white hairs. The hair was then rinsed, washedwith a standard shampoo and then dried.

The hair was dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing.

EXAMPLE 14

The ready-to-use dye compositions below are prepared (contents ingrams):

Compositions 1(G) 2(G) 3(G) 4(G) 5(G) 6(G) Para-phenylenediamine 0.70 —0.38 0.55 — 0.283 para-Aminophenol 0.187 — 0.147 — 5-N-(β-Hydroxyethyl)0.21 0.36 — 0.165 0.283 amino-2-methylphenol Cationic dye of example 40.6 0.065 0.12 0.47 0.051 0.094 Uricase from Arthrobacter 1.5 1.5 1.5 —— — globiformis, at 20 inter- national units (I.U.)/mg. sold by thecompany Sigma Uric acid 1.5 1.5 1.5 — — — Laccase issue from Rhus 1.81.8 1.8 vemicifere laccase*** at 180 international units (I.U.)/mg soldby the company Sigma Common dye support (*) (*) (*) (*) — — — Common dyesupport (**) — — — (**) (**) (**) Demineralized water qs 100 100 100 — —— Demineralized water qsq — — — 100 100 100 ***possibility of exchangeof Laccasa issue de Rhus vemicifere laccasa*** at 180 internationalunits (I.U./mg. sold by the company Sigma with 1% of pyricularia orizaeat 100 units/mg. sold by the company I.C.N. (*) Common dye supportEthanol 20.0 g Hydroxyethylcellulose sold under the name Natrosol 1.0 g250 HR ® by the company Aqualon Poly(C₈-C₁₆)alkylglucoside as an aqueoussolution 8.0 g containing 60% active material (A.M.) buffered withammonium citrate (0.5%), sold under the name Oramix CG110 ® by thecompany SEPPIC Monoethanolamine qs pH = 9 (**) Common dye supportEthanol 20.0 g Poly(C₈-C₁₆)alkylglucoside as an aqueous solution 4.8 gcontaining 60% active material (A.M.) buffered with ammonium citrate(0.5%), sold under the name Oramix CG110 ® by the company SEPPIC pHagent Qs pH = 6.5

Compositions 7(G)^(I) to 32(G)^(I) are identical to composition 1(G),and compositions 7(G)^(II) to 32(G)^(II) are identical to composition3(G), and compositions 7(G)^(III) to 32(G)^(III) are identical tocomposition 4(G), and compositions 9(G)^(IV) to 32(G)^(IV) are identicalto composition 6(G), as given above in example 4 with the proviso thatpara-phenylenediamine is replaced by a compound H as given below intable 1.

TABLE 1 Com- positions Compound H 7(G)^(I-IV) para-toluylenediamine9(G)^(I-IV) 2-chloro-para-phenylendiamine 10(G)^(I-IV)2,3-dimethyl-para-phenylenediamine 11(G)^(I-IV)2,6-dimethyl-para-phenylenediamine 12(G)^(I-IV)2,6-diethyl-para-phenylenediamine 13(G)^(I-IV)2,5-dimethyl-para-phenylenediamine 14(G)^(I-IV)N,N-dimethyl-para-phenylenediamine 15(G)^(I-IV)N,N-diethyl-para-phenylenediamine 16(G)^(I-IV)N,N-dipropyl-para-phenylenediamine 17(G)^(I-IV)4-amino-N,N-diethyl-3-methylaniline 18(G)^(I-IV)N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine 19(G)^(I-IV)4-amino-N,N-bis(.beta.-hydroxyethyl)-3-methylaniline 20(G)^(I-IV)4-amino-3-chloro-N,N-bis(.beta.-hydroxyethyl)aniline 21(G)^(I-IV)2-.beta.-hydroxyethyl-para-phenylenediamine 22(G)^(I-IV)2-fluoro-para-phenylenediamine 23(G)^(I-IV)2-isopropyl-para-phenylenediamine 24(G)^(I-IV)N-(.beta.-hydroxypropyl)-para-phenylenediamine 25(G)^(I-IV)2-hydroxymethyl-para-phenylenediamine 26(G)^(I-IV)N,N-dimethyl-3-methyl-para-phenylenediamine 27(G)^(I-IV)N,N-(ethyl-.beta.-hydroxyethyl)-para-phenylenediamine 28(G)^(I-IV)N-(.beta.,.gamma.-dihydroxypropyl)-para-phenylenediamine 29(G)^(I-IV)N-(4′-aminophenyl)-para-phenylenediamine 30(G)^(I-IV)N-phenyl-para-phenylenediamine 31(G)^(I-IV)2-.beta.-hydroxyethyloxy-para-phenylenediamine 32(G)^(I-IV)2-.beta.-acetylaminethyloxy-para-phenylenediamine

Compositions 100(G)^(I) to 110(G)^(I) are identical to composition 2(G),and compositions 200(G)^(II) to 210(G)^(II) are identical to composition5(G), the proviso that para-aminophenol is replaced by a compound H asgiven below in table 2.

TABLE 2 Compositions Compound H 200(G)^(I-II) 4-amino-3-methylphenol203(G)^(I-II) 4-amino-3-fluorophenol 204(G)^(I-II)4-amino-3-hydroxymethylphenol 205(G)^(I-II) 4-amino-2-methylphenol206(G)^(I-II) 4-amino-2-hydroxymethylphenol 207(G)^(I-II)4-amino-2-methoxymethyl-phenol 208(G)^(I-II) 4-amino-2-aminomethylphenol209(G)^(I-II) 4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol210(G)^(I-II) 4-amino-2-fluoro-phenol

Each of the ready-to-use dye compositions are applied for 30 minutes.The hair was then rinsed, washed with a standard shampoo and then dried.

The locks of hair are dyed in brilliant red-tinged violet shade.

EXAMPLE 15

The ready-to-use dye compositions below were prepared (contents ingrams):

Compositions 1(I) 2(I) 3(I) Behenyl-trimethyl- — 2.0 A.M. — ammonimumcloride Cetyl-trimethylammonimum — — 2.0 A.M. cloride Ethanol 10 10 10Cationic dye of example 1 0.20 0.20 0.10 2-Amino-2-methyl-1-propanol pH9 pH 9 pH 9 qs Demineralized water qs 100 100 100

Each of the ready-to-use dye compositions are applied for 30 minutes.The hair was then rinsed, washed with a standard shampoo and then dried.

The locks of hair were dyed in brilliant red-tinged violet shade.

Compositions 4(I) to 20(I) are identical to composition 2(I), theproviso that behenyl-trimethylammonimum cloride is replaced by acompound H′ as given below in table 2.

TABLE 2 Compo- sitions Compound H^(I) 4(I) tetramethylammonium chloride5(I) diethyl-dimethylammonium chloride 6(I) methyl-trimethylammoniumchloride 7(I) ethyl-trimethylammonium chloride 8(I)distearyl-dimethylammonium cloride 9(I)oleocetyldimethylhydroxyethylammonium chloride 10(I)oleocetylhydroxyethylammonium chloride 11(I)stearamidopropyldimetylammonium chloride sold under the name CERAPHYL 70by the company VAN DYK 12(I)2-hexyldecylamino-1-methyl-1′-N-(ethylcarbamaic acidhexyldecylamine)-imidazolium methylsulphate sold under the name REWOQUATW 7500 by the company REWO 13(I) propylen-1,3-diammonium chloride 14(I)propylen-1,3-diammonium bromide 15(I) propylen-1,3-diammonium phosphate16(I) propylen-1,3-diammonium sulphate 17(I) propylen-1,3-diammoniumacetat 18(I) propylen-1,3-di-trimetylammonium chloride 19(I)propylen-1,3-di-trimetylammonium sulphate 20(I)propylen-1,3-di-trimetylammonium acetate

Compositions 1(I)′ to 20(I)′ are identical to compositions 1(I) to20(I), with the proviso that ethanol is replaced by isopropanol.

Compositions 1(I)″ to 15(I)″ are identical to compositions 1(I) to 20(I)and 1(I)′ to 20(I)′, with the proviso that 2-amino-2-methyl-1-propanolis replaced by a basifying agent D′.

Compositions 1(I)^(II) to 15(I)^(II) basifying agent D′ 1(I)^(II)pottassium carbonate 2(I)^(II) sodium carbonate 3(I)^(II)triethanolamine 4(I)^(II) diethanolamine 5(I)^(II) monoethanolamine6(I)^(II) sodium hydroxide 7(I)^(II) potassium hydroxide 8(I)^(II)N,N-dimethyl-N′-ethylenediamine 9(I)^(II) 4-(Ethylamino)-b-butylamine10(I)^(II) N-(n-Propyl)-1,3-propanediamine 11(I)^(II)N,N-diethylenediamine 12(I)^(II) N,N,N′,N′-Tetramethylethylenediame13(I)^(II) N,N-dimethylthydrazine 14(I)^(II) 2-n-butylaminoethylamine15(I)^(II) 1,5-diaminohexane

EXAMPLE 16

The ready-to-use dye compositions below are prepared (contents ingrams):

Composition 1(L) 2(L) 2-Amino-5-hydroxy- 0.35 — nitrobenzene2-N-(β-Hydroxyethyl) — 0.25 amino-5-aminonitrobenzene Cationic dye*0.065 0.04 Common dye support (*) (*) (*) Demineralized water qs 100 100(*) Common dye support Ethanol 20.0 g Nonylphenoloxyethylen with 9 moloxyethylen  8.0 g sold under the name IGEPAL NR 9 Or by the companyRHODIA CHEMIE 2-Amino-2-methyl-1-propanol qs. pH = 9.5 *Cationic dye ismixed with the other components of the oxidative dye composition shortlybefore the applying to the hair. *Cationic dye is a single cationic dyeor composition of cationic dyes as given above compositions (V′) =compositions (V′)′ = composition 1L + composition 2L + *Cationic dye*cationic dye *cationic dye Cationic dye of example 1 10(V′) 10(V′)′Cationic dye of example 2 11(V′) 11(V′)′ Cationic dye of example 312(V′) 12(V′)′ Cationic dye of example 4 13(V′) 13(V′)′ compositions(V′) = composition 1L + *cationic dye + **dye (*cationic dye/**dye in aratio of 1:1) cationic dye of cationic dye cationic dye cationic dye of**Dye example 1 of example 2 of example 3 example 4 HC Yellow 2  14(V′) 15(V′)  16(V′)  17(V′) HC Yellow 4  18(V′)  19(V′)  20(V′)  21(V′) HCYellow 6  22(V′)  23(V′)  24(V′)  25(V′) Basic Yellow 57  26(V′)  27(V′) 28(V′)  29(V′) Basic Yellow 9  30(V′)  31(V′)  32(V′)  33(V′) DisperseOrange 3  34(V′)  35(V′)  36(V′)  37(V′) HC Red 3  38(V′)  39(V′) 40(V′)  41(V′) HC Red BN  42(V′)  43(V′)  44(V′)  45(V′) Basic Red 76 46(V′)  47(V′)  48(V′)  49(V′) Basic Red 2  50(V′)  51(V′)  52(V′) 53(V′) Basic Violet 14  54(V′)  55(V′)  56(V′)  57(V′) Basic Blue 3 58(V′)  59(V′)  60(V′)  61(V′) Basic Blue 6  62(V′)  63(V′)  64(V′) 65(V′) Basic Blue 7  66(V′)  67(V′)  68(V′)  69(V′) Basic Blue 9 70(V′)  71(V′)  72(V′)  73(V′) Basic Blue 12  74(V′)  75(V′)  76(V′) 77(V′) Basic Blue 26  78(V′)  79(V′)  80(V′)  81(V′) HC Blue 2  82(V′) 83(V′)  84(V′)  85(V′) HC Blue 7  86(V′)  87(V′)  88(V′)  89(V′) HCBlue 12  90(V′)  91(V′)  92(V′)  93(V′) Disperse Blue 3  94(V′)  95(V′) 96(V′)  97(V′) HC Violet 1  98(V′)  99(V′) 100(V′) 101(V′) DisperseViolet 1 102(V′) 103(V′) 104(V′) 105(V′) Disperse Black 9 106(V′)107(V′) 108(V′) 109(V′) Basic Brown 16 110(V′) 111(V′) 112(V′) 113(V′)Basic Brown 17 114(V′) 115(V′) 116(V′) 117(V′)2-amino-6-chloro-4-nitrophenol 118(V′) 119(V′) 120(V′) 121(V′)4-amino-2-nitrodiphenylamine- 122(V′) 123(V′) 124(V′) 125(V′)2′-carboxylic acid 6-nitro-1,2,3,4-tetrahydroquinoxaline 126(V′) 127(V′)128(V′) 129(V′) 4-N-ethyl-1,4- 130(V′) 131(V′) 132(V′) 133(V′)bis(2′-hydroxyethylamino)-2- nitrobenzene hydrochloride1-methyl-3-nitro-4- 135(V′) 136(V′) 137(V′) 138(V′)(2′-hydroxyethyl)-aminobenzene compositions (V′) = composition 1L +*cationic dye + ***dyes (*cationic dye/***dye in a ratio of 1:1)cationic dye of cationic dye cationic dye cationic dye of Dyes ***example 1 of example 2 of example 3 example 4 HC Yellow 2, HC Yellow 4139(V′) 140(V′) 141(V′) 142(V′) Basic Red 76, HC Red BN, 143(V′) 144(V′)145(V′) 146(V′) HC Red BN, Basic Violet 14 147(V′) 148(V′) 149(V′)150(V′) Basic Blue 12, Basic Blue 6 151(V′) 152(V′) 153(V′) 154(V′)4-N-ethyl-1,4- 155(V′) 156(V′) 157(V′) 158(V′)bis(2′-hydroxyethylamino)- 2-nitrobenzene hydrochloride,6-nitro-1,2,3,4-tetrahydroquinoxaline Basic Brown 16, Disperse Black 9159(V′) 160(V′) 162(V′) 163(V′) compositions (V′) = composition 1L +*cationic dye + ****dyes (*cationic dye/****dye in a ratio of 1:1)cationic dye of cationic dye cationic dye cationic dye of Dyes ****example 1 of example 2 of example 3 example 4 HC Yellow 2, HC Yellow 4,164(V′) 165(V′) 166(V′) 167(V′) Basic Red 2 Basic Red 76, HC Red BN,168(V′) 169(V′) 170(V′) 171(V′) Basic Red 2 HC Red BN, Basic Violet 14,172(V′) 173(V′) 174(V′) 175(V′) Disperse Violet 1 Basic Blue 12, BasicBlue 6, 176(V′) 177(V′) 178(V′) 179(V′) Disperse Violet 12-amino-6-chloro-4-nitrophenol, 180(V′) 181(V′) 182(V′) 183(V′)6-nitro-1,2,3,4-tetrahydroquinoxaline, Basic Brown 17 Basic Brown 16,Disperse Black 9, 184(V′) 185(V′) 186(V′) 187(V′) Basic Brown 17compositions (V′) = composition 1L + *cationic dye + *****dyes(*cationic dye/*****dye in a ratio of 1:1) cationic dye of cationic dyecationic dye cationic dye of Dyes ***** example 1 of example 2 ofexample 3 example 4 HC Yellow 2, Basic Red 76, 188(V′) 189(V′) 190(V′)191(V′) Basic Red 2, Disperse Orange 3 Basic Red 76, HC Red BN, 192(V′)193(V′) 194(V′) 195(V′) Basic Red 2, Basic Violet 14 HC Red BN, BasicViolet 14, 196(V′) 197(V′) 197(V′) 198(V′) Disperse Violet 1, HC Red 3Basic Blue 12, Basic Blue 6, 199(V′) 200(V′) 201(V′) 202(V′) DisperseViolet 1, Basic Blue 9 2-amino-6-chloro-4-nitrophenol, 203(V′) 204(V′)205(V′) 206(V′) 6-nitro-1,2,3,4-tetrahydroquinoxaline, Basic Brown 17,HC Red BN Basic Brown 16, Disperse Black 9, 207(V′) 208(V′) 209(V′)210(V′) Basic Brown 17, Basic Red 76

Each of the ready-to-use dye compositions are applied for 30 minutes.The hair is then rinsed, washed with a standard shampoo and then dried.

The locks of hair are dyed in brilliant shades.

EXAMPLE 17

The powdery dye composition 1(M) is prepared as given below:

Composition 1(M) (%-by weight) Hydroxypropyl-Guar-triamoniumchloride20.00 Cycloocatamylose 4.00 PEG-150/PPG 301 16.00 Polyethylenglycol (MW10000) 48.20 Corn proteine hydrolysate 5.00 Honey dried extract 2.00Potassium sorbat 2.00 Cationic dye of formula (I) of example 1 0.2

An oxidative dye powder for hair, composition 2(M), is prepared as givenbelow:

Composition 2(M) (%-by weight) p-Toluylendiaminsulphate 3.0 Rasorcine1.0 3-Aminophenolsulphate 0.3 m-Phenylendiamine hydrochloride 0.2Silicon dioxide 0.5 sodium lauryl sulphate 0.2 sodium alginate 3.5sodium meta silica 0.4 potassium sulphite 0.1

Compositions 2(M)′ to 33(M)′ are identical to composition 2(M), with theproviso that resorcine is replaced by a compound M′ as given in thetable below.

Compositions 2(M)″ to 33(M)″ are identical to composition 2(M), with theproviso that m-phenylendiamine hydrochloride is replaced by a compoundM′ as given in the table below.

Compositions 2(M)′″ to 33(M)′″ are identical to composition 2(M), withthe proviso that 3-aminophenolsulphate is replaced by a compound M′ asgiven in the table below.

Compositions 2(M)^(IV) to 33(M)^(IV) are identical to composition 2(M),with the proviso that 3-aminophenolsulphate, m-phenylendiaminehydrochloride and resorcine is replaced by 1.5%-by weight of a compoundM′ as given in the table below.

Composition 2(M) compound M′  1(M)^(HV) 2-methylresorcine  2(M)^(HV)4-chloroesorcine  3(M)^(HV) 2-amino-4-chlorophenol  4(M)^(HV)4-(N-methyl)aminophenol  5(M)^(HV) 2-aminophenol  6(M)^(HV)3-aminophenol  7(M)^(HV) 1-methyl-2-hydroxy-4-aminobenzene  8(M)^(HV)3-N,N-dimethylaminophenol  9(M)^(HV) 4-amino-3-methylphenol 10(M)^(HV)5-amino-2-methylphenol 11(M)^(HV) 6-amino-3-methylphenol 12(M)^(HV)3-amino-2-methylamino-6-methoxypyridine 13(M)^(HV)2-amino-3-hydroxypyridine 14(M)^(HV) 4-aminodiphenylamine 15(M)^(HV)4,4′-diaminodophenylamine 16(M)^(HV) 2-dimethylamino-5-aminopyridine17(M)^(HV) 2,6-diaminopyridine 18(M)^(HV) 1,3-diaminobenzol 19(M)^(HV)1-amino-3-(2′-hydroxyethylamino)benzene 20(M)^(HV)1-amino-3-[bis(2′-hydroxyethyl)amino]benzene 21(M)^(HV)1,3-diaminotoluene 22(M)^(HV) α-naphthol 23(M)^(HV)1,4-diamino-2-chlorobenzene 24(M)^(HV) 4,6-dichlororesorcine 25(M)^(HV)4-hydroxy-1,2-methylendioxybenzene 26(M)^(HV) 1,5-dihydroxynaphthaline27(M)^(HV) 1,7-dihydroxynaphthaline 28(M)^(HV) 2,7-dihydroxynaphthaline29(M)^(HV) 1-hydroxynaphthaline 30(M)^(HV)4-hydroxy-1,2-methylenedioxybenzene 31(M)^(HV)2,4-diamino-3-chlorophenol 32(M)^(HV)1-methoxy-2-amino-4-(2′-hydroxyethylamino)- benzene 33(M)^(HV)2,4-diamino-3-chlorophenol and 1-methoxy-2-amino-4-(2′-hydroxyethylamino)-benzeneDying Process

-   -   a) Bleached human hair is pretreated with a common permanent        wave on the basis of thioglycolic acid at a pH value in the        range of 9.0 to 9.5 and then rinsed with water. Afterwards, the        hair is treated with the powdery dye composition 1(M) or        1(M)^(I-IV) to 33(M)^(I-IV) and 40 ml stabilized peroxide        solution (6% by weight).

The powdery dye composition is applied for 5 to 10 minutes and thenrinsed with water and in following, dried.

The hair is dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing.

-   -   b) A fixing solution, composition 3(M), is prepared as given        below.

fixing solution, composition 3(M) (%-by weight) Peroxide solution 4.8PPG30/PEG 150 1.0 Cocosamineoxide 0.6 Coco fatty acid/collagenhydrolysate, 0.5 potassium salt Polyquatemium-35 0.5 Sodiumphosphate 0.4Phosphore acid 0.3 Citronic acid 0.3 Demineralized Water qs 100

10 g of composition 2(M) is mixed with 80 ml of composition 3(M). Theresulting mixture is applied on bleached human hair, which waspretreated with a common permanent wave on the basis of thioglycolicacid at a pH value in the range of 9.0 to 9.5 for 10 minutes. Afterwarsthe hair is rinsed and dried.

The hair is dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing.

This oxidative dying process is also applicable if it is divided in twosteps:

-   step 1: prefixing with peroxide, and then the removal of rollers-   step 2: after fixing with dying.

EXAMPLE 18

The ready-to-use dye compositions below are prepared (contents ingrams):

Compositions 1(N) 2(N) 3(N) 4(N) Hydroxyethylcellulose sold 1.0 underthe name A.M. NATROSOL 250 HHR by the company AQUALONCarboxymethylcellulose sold 1.0 under the name A.M. BLANOSE 7M by thecompany AQUALON Resin of guar sold under the 1.0 name VIDOGUM GH175 byA.M. the company UNIPECTINE Resin of scleroglucane sold 1.0 under thename AMIGEL by A.M. the company ALBAN MULLER INTERNATINAL Ethanol 10 1010 10 2-Amine-2-methyl-1-propanol pH 9 pH 9 pH 9 pH 9 Cationic dye offormula (I) of 0.2 0.2 0.2 0.2 example 1 Demineralized water qs 100 100100 100

Each of the ready-to-use dye compositions are applied for 30 minutes tolocks of natural grey hair containing 90% white hairs. The hair is thenrinsed, washed with a standard shampoo and then dried.

The locks of hair are dyed in brilliant red-tinged violet shade.

Compositions 5(N)″ to 119(N)″ are identical to compositions 1(N) to4(N), with the proviso that 2-amino-2-methyl-1-propanol is replaced by abasifying agent N′.

compositions basifying agent N′  5(N)^(II) potassium carbonate 6(N)^(II) sodium carbonate  7(N)^(II) triethanolamine  8(N)^(II)diethanolamine  9(N)^(II) monoethanolamine 10(N)^(II) sodium hydroxide11(N)^(II) potassium hydroxide 12(N)^(II)N,N-dimethyl-N′-ethylenediamine 13(N)^(II) 4-(ethylamino)-b-butylamine14(N)^(II) N-(n-propyl)-1,3-propanediamine 15(N)^(II)N,N-diethylenediamine 16(N)^(II) N,N,N′,N′-Tetramethylethylenediamine17(N)^(II) N,N-dimethylhydrazine 18(N)^(II) 2-n-butylaminmoethylamine19(N)^(II) 1,6-diaminohexane

Composition 20(N)″ is identical to compositions 1(N) and 5(N)″ to19(N)″, with the proviso that hydroxyethylcellulose is replaced by ahydroxypropylcellulose.

EXAMPLE 19

Permanent wave composition consisting of two compositions O, 1(O)-5(O),and P, 1(P)-5(P).

% by weight Composition 1(O) Cationic dye of formula (I) 0.2 35-volumeshydrogen peroxide solution 4.3 Cetanol 0.5 Hydrated lanoline 0.35Actealdehyde 0.02 Sodiumpyrophphate 0.025 Phosphoric acid, purifiedwater(with 100 phosphoric acid adjusted to pH 6.5) Composition 1(P)Ammoniumthioglycolate solution 13.6 (50% by volumes thioglycolic acid)Ammoniumcicarbonate 3.5 Disodiumedetat 0.1 Monoethanolamine, purifiedwater(with 100 monoethanolamine adjusted to pH 6.5)Process:

According to common processes, white hair, which tips are wrapped up inpaper, is rolled up on a stick of synthetic material (sick with 1.5 cmin diameter). This stick is then dipped in the composition 1(P) for 15minutes at 30° C., and afterwards rinsed with water for 1 minute. Thenthe stick is dipped in the composition 01 for 15 minutes at 30° C. andafterwards rinsed with water, washed with a standard shampoo and thendried. In this way the white hair is homogeneously dyed and waved fromthe roots up to the tips.

% by weight Composition 2(O) Cationic dye of formula (I) of example 10.2 Potassiumbromate 10.2 Lauryldimethylacetic acid betain 1.0Cetyltrimethylammoniumchloride 0.6 Sodiumbenzoate 0.3 Salicylacid 0.05Trisodiumphosphate 0.27 Phosphoric acid, purified water(with 100phosphoric acid adjusted to pH 6.5) Composition 2(P) L-Cysteinehydrochloride 7.0 Cetanol 0.5 Oteytalcohol 0.5 Polyoxyethylenethter (10UO) 1.0 Polyoxyetheylencetylether (15 UO) 1.0 Sodiumedetart 0.1Monoethanolamine, purified water (with 100 monoethanolamine adjusted topH 9)

White hair is treated in the same way as given above in the process ofexample 9 with the proviso that 1(P) is replaced by 2(P) and 1(O) isreplaced by 2(O).

% by weight Composition 3(O) Cationic dye of formula (I) of example 10.2 Uricase (20 U/mg) 1.0 Uric acid 1.0 Glycerine 3.0 Purified water qs100 Composition 3(P) Ammoniumthioglycolate solution (50% by 7.0 volumesthioglycolic acid) Polyoxyethylenether (10 UO) 1.0Polyoxyetheylencetylether (15 UO) 1.0 Sodiumlaurylsulphate 0.5 Collagenhydrolysate solution 0.4 Disodiumedetat 0.1 Ammonia water, purifiedwater(with 100 Ammonia water, adjusted to pH 9)

White hair is treated in the same way as given above in the process ofexample 9 with the proviso that 1(P) is replaced by 3(P) and 1(O) isreplaced by 3(O).

% by weight Composition 4(O) Cationic dye of formula (I) of example 10.4 Monoethanolamine, purified water (with 100 monoethanolamine adjustedto pH 8) Composition 4(P)/ oxiative fixing formulation Sodiumbromate17.0 Lauryldimethylaceticacidbetain 1.5 Cetyltrimethylammoniachloride1.0 Sodiumbenzoate 0.6 Salicylicacid 0.1 Trisodiumphophate 0.54Phosphoric acid, purified water(with 100 phosphoric acid adjusted to pH6.5)

White hair is treated in the same way as given above in the process ofexample 9 with the proviso that 1(P) is replaced by 3(P) and 1(O) isreplaced by a mixture of the two compositions 4(O) and 4(P) in a ratioof 1:1.

% by weight Composition 5(O) Cationic dye of formula (I) of example 10.2 % by weight in relation to the composition P5 Composition 5(P)/oxidative fixing formulation Sodiumbromate 8.5Lauryldimethylaceticacidbetain 1.0 Cetyltrimethylammoniachloride 0.6Sodiumbenzoate 0.3 Salicylicacid 0.05 Trisodiumphosphate 0.27 Phosphoricacid, purified water(with 100 phosphoric acid adjusted to pH 6.5)

White hair is treated in the same way as given above in the process ofexample 9 with the proviso that 1(P) is replaced by 3(P) and 1(O) isreplaced by a mixture of the two compositions 5(O) and 5(P) in a ratioof 1:10.

Composition 6(O) % by weight Cationic dye of formula (I) of example 10.2 Hydroxyethylcallulose 2.5 Triethanolamine, purified water(with 100triethanolamine adjusted to pH 8.0) qs

White hair which is treated with the above cited compositions ishomogeneously waved and dyed in a brilliant red-tinged violet shade.

EXAMPLE 20

The ready-to-use dye compositions below are prepared (contents ingrams):

Compositions 1(Q) 2(Q) 3(Q) 4(Q) 5(Q) Cationic dye of 0.2 0.2 0.15 0.120.1 formula (I) of example 1 Cocoglutamate of 5.0 triethanolamine soldA.M. under the name ACYGLUTAMATE CT12 by the company AJINOMOTOLaurylsarcorsinate 5.0 of sodium sold A.M. under the name ORAMIX L30 bythe company SEPPIC Cocoylicethionate of 5.0 sodium sold under A.M. thename JORDAPON POWDER by the company PPG Laurylether 5.0 carboxilic acid(10 A.M. UO) sold under the name AKYPO RLM 100 by the company KAO Sodiumsalt of 5.0 Tartaric ester of A.M. cocoylpolyglycoside sold under thename GUCAROL AGE ET by the company CESALPINE Ethanol 10 10 10 10 102-Amine-2-methyl- pH 9 pH 9 pH 9 pH 9 pH 9 1-propanol qs Demineralized100 100 100 100 100 water qsq

The resulting compositions are applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The hair is then rinsed,washed with a standard shampoo and then dried.

The hair is dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing.

Compositions 6(Q)″ to 20(Q)″ are identical to compositions 1(Q) to 5(Q),with the proviso that 2-amino-2-methyl-1-propanol is replaced by abasifying agent Q′.

compositions basifying agent Q′  6(Q)^(II) potassium carbonate 7(Q)^(II) sodium carbonate  8(Q)^(II) triethanolamine  9(Q)^(II)diethanolamine 10(Q)^(II) monoethanolamine 11(Q)^(II) sodium hydroxide12(Q)^(II) potassium hydroxide 13(Q)^(II)N,N-dimethyl-N′-ethylenediamine 14(Q)^(II) 4-(ethylamino)-b-butylamine15(Q)^(II) N-(n-propyl)-1,3-propanediamine 16(Q)^(II)N,N-diethylenediamine 17(Q)^(II) N,N,N′,N′-Tetramethylethylenediamine18(Q)^(II) N,N-dimethylhydrazine 19(Q)^(II) 2-n-butylaminmoethylamine20(Q)^(II) 1,6-diaminohexane

Composition 21(Q)′ is identical to compositions (Q) and (Q)″, with theproviso that ethanol is replaced by a isopropanol.

EXAMPLE 21

The ready-to-use dye compositions below are prepared (contents ingrams):

Compositions 1(R) 2(R) 3(R) 4(R) 5(R) 6(R) (7R) 8(R) Cationic dye 0.120.1 0.11 0.12 0.20 0.10 0.20 0.15 of formula (1) of example 1 Alkylpoly-8.0 8.0 glucoside sold under the name ORAMIX CG110 by the company SEPPICN-Decanonyl- 8.0 8.0 N-methyl- glucamine** O-Hexa- 8.0 8.0 decaniyl-6-αD-glucose N-Cocolacto- 8.0 8.0 bionamide Ethanol 10 10 10 10 10 10 1010 2-Amine-2- pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 methyl-1- propanolqs Demineralized 100 100 100 100 100 100 100 100 water qsq**N-decanoyl-N-methylglucamine (acid amide of polyhydroxy of the formulaC₉H₁₉—CO—N(CH₃)—CH₂—(CHOH)₄—CH₂OH)

The resulting compositions are applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The hair is then rinsed,washed with a standard shampoo and then dried.

The hair is dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing.

Compositions 10(R)′ to 24(R)′ are identical to compositions 1(R) to8(R), with the proviso that 2-amino-2-methyl-1-propanol is replaced by abasifying agent R′.

compositions basifying agent R^(I) 10(R)^(I) potassium carbonate11(R)^(I) sodium carbonate 12(R)^(I) triethanolamine 13(R)^(I)diethanolamine 14(R)^(I) monoethanolamine 15(R)^(I) sodium hydroxide16(R)^(I) potassium hydroxide 17(R)^(I) N,N-dimethyl-N′-ethylenediamine18(R)^(I) 4-(ethylamino)-b-butylamine 19(R)^(I)N-(n-propyl)-1,3-propanediamine 20(R)^(I) N,N-diethylenediamine21(R)^(I) N,N,N′,N′-Tetramethylethylenediamine 22(R)^(I)N,N-dimethylthydrazine 23(R)^(I) 2-n-butylaminoethylamine 24(R)^(I)1,6-diaminohexane

Compositions 26(R)^(II) to 39(R)^(II) are identical to compositions 1(R)to 8(R), with the proviso that alkylpolyglucoside is replaced by acompound R^(II).

compositions compound R^(II) 26(R)^(II) APG 300* 27(R)^(II) APG 350*28(R)^(II) APG 500* 29(R)^(II) APG 550* 30(R)^(II) APG 625* 31(R)^(II)APG base 10-12* 32(R)^(II) ORAMIX CG 110** 33(R)^(II) ORAMIX NS 10**34(R)^(II) LUTENSOL GD 70 sold by company BASF 35(R)^(II) PLANTAREN1200*** 36(R)^(II) PLANTAREN 1300*** 37(R)^(II) PLANTAREN 2000***38(R)^(II) PLANTACARE 818*** 39(R)^(II) PLANTACARE 1200*** *sold bycompany HENKEL **sold by company SEPPIC ***sold by company HENKEL

Compositions 40(R)^(III) to 52(R)^(III) are identical to compositions(R), (R)^(I) and (R)^(II) with the proviso thatO-hexadecanoyl-6-αD-glucose is replaced by a compound R^(III).

com- positions compound R^(III) 40(R)^(III) O-Octanoyl-6-D-glucose41(R)^(III) O-Oleyl-6-D-glucose 42(R)^(III) O-Linoleyl-6-D-glucose43(R)^(III) monostearate methylglucoside 44(R)^(III) sesquistearatemethylglucoside 45(R)^(III) decanoate ethyl-6-glucoside 46(R)^(III) monoand dicocoate(82/7) ethyl-6-glucoside sold under the name BIOSURF COCOby the company NOVO 47(R)^(III) mono and dilaurate (84/8)ethyl-6-glucoside sold under the name BIOSURF 12 by the company NOVO48(R)^(III) monococoate butylglucoside polyoxyethylene with 3 moloxygen/ethylen sold under the name REWOPOL V3122 by the company REWO49(R)^(III) monococoate butylglucoside sold under the name REWOPOL V3101by the company NOVO REWOSAN V3101 by the company NOVO 50(R)^(III)monococoate butylglucoside sold under the name REWOSAN V3101 by thecompany NOVO 51(R)^(III) monolaurate of saccharose 52(R)^(III)monococoate of saccharose

Composition 25(R)′ is identical to any of a composition (R) (R)″ and(R)′″, with the proviso that ethanol is replaced by a isopropanol.

EXAMPLE 22

The dye compositions below are prepared (contents in grams):

Compositions 1(S) 2(S) Cationic dye formula (I) of example 1 0.2 0.2Propylene gylcol 10.0 2-Amine-2-methyl-1-propanol qs pH 9 Demineralizedwater qsq 100 100 Monomethylether of propylene glycol 10.0

The resulting compositions 1 or 2 are applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The hair is then rinsed,washed with a standard shampoo and then dried.

The hair is dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing.

Compositions 3(S)^(I) to 17(S)^(I) are identical to compositions 1(S),with the proviso that propylene glycol is replaced by a compound S′.

compositions compound S^(I) 3(S)^(I) glycerine 4(S)^(I) 1,3-propanediol5(S)^(I) 2-butene-1,4-diol 6(S)^(I) pentane-1,5-diol 7(S)^(I)2,2-dimethyl-propane-1,3-diol 8(S)^(I) 3-methyl-pentane-1,5-diol9(S)^(I) potassium hydroxide 10(S)^(I) pentane-1,2-diol 11(S)^(I)2,2,4-trimethyl-pentane-1,3-diol 12(S)^(I) 2-methylpropane-1,3-diol13(S)^(I) hexyleneglycol 14(S)^(I) 1,3-butyleneglycol 15(S)^(I)dipropyleneglycol 16(S)^(I) diethylenglcol 17(S)^(I) triethylenglycol

Compositions 18(S)^(II) to 29(S)^(II) are identical to compositions2(S), with the proviso that monomethylether of propylene glycol isreplaced by a compound S^(II).

compositions compound S^(II) 18(S)^(II) monoethylether of propyleneglycol 19(S)^(II) dimethylether of isopropylene glycol 20(S)^(II)monomethylether of diethylen glycol 21(S)^(II) monomethylether ofdipropylen glycol 22(S)^(II) monomethylether of tripropylen glycol23(S)^(II) monomethylether of dimethylen glycol 24(S)^(II)monomethylether of diethylen glycol 25(S)^(II) monophenylether ofethylen glycol 26(S)^(II) monobenylether of ethylen glycol 27(S)^(II)monophenylether of propylene glycol 28(S)^(II) monophenylether ofdiethylen glycol 29(S)^(II) monobenylether of diethylen glycol

Compositions 30(S)^(III) to ₄₄(S)^(III) are identical to compositions1(S), (S)^(I) and (S)^(II), with the proviso that2-amino-2-methyl-1-propanol is replaced by a basifying agent S^(III).

compositions basifying agent S^(III) 30(S)^(III) pottassium carbonate31(S)^(III) sodium carbonate 33(S)^(III) triethanolamine 34(S)^(III)diethanolamine 35(S)^(III) monoethanolamine 36(S)^(III) sodium hydroxide37(S)^(III) potassium hydroxide 38(S)^(III)N,N-dimethyl-N′-ethylenediamine 39(S)^(III) 4-(ethylamino)-b-butylamine40(S)^(III) N-(n-propyl)-1,3-propanediamine 41(S)^(III)N,N-diethylenedimine 42(S)^(III) N,N,N′,N′-tetramethylethylenediamine43(S)^(III) N,N-dimethylhydrazine 44(S)^(III) 2-n-butylaminoethylamine45(S)^(III) 1,6-diaminohexane

EXAMPLE 23

The ready-to-use dye compositions below are prepared (contents ingrams):

Compositions 1(T) 2(T) 3(T) Monobromohydrate of 5,6- 0.7 dihydroxyindoline 5,6-dihydroxy indole 0.5 1,2,4-Trihydroxy benzene 1.2 Cationicdye of formula (I) of 0.1 0.07 0.05 example 1 Common dye support (*) (*)(*) (*) Demineralized water q.s.q 100 100 100 (*) Common dye support:Ethanol 20.0 g Nonylphenoloxyethylen with 9 mol oxyethylen 8.0 g soldunder the name IGEPAL NR 9 Or by the company RHODIA CHEMIE2-Amino-2-methyl-1-propanol qs. ph = 8.0

Each of the ready-to-use dye compositions are applied for 30 minutes tolocks of natural grey hair containing 90% white hairs. The hair is thenrinsed, washed with a standard shampoo and then dried.

The hair is dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing.

Compositions 4(T)^(I) to 9(T)^(I) are identical to compositions 3(T),with the proviso that 1,2,4-trihydroxy benzene is replaced by a compoundT^(I).

Compositions compound T^(I) 4(T)^(I) 1-methyl-2,4,5-trihydroxy benzene5(T)^(I) 2,4-diamino-6-methyl phenol 6(T)^(I) 2-amino-4-methylaminophenol 7(T)^(I) 2,4-diamino-4-methyl phenol 8(T)^(I)2,6-diamino-4-diethylamino phenol 9(T)^(I) 2,6-diamino-1,4-dihydroxybenzene

Compositions 10(T)^(II) to 17(T)^(II) are identical to compositions2(T), with the proviso that 5.6-dihydroxy indole is replaced by acompound T^(II).

compositions compound T^(II) 10(T)^(II) 2-methyl-5,6-dihydroxy indole11(T)^(II) 3-methyl-5,6-dihydroxy indole 12(T)^(II)1-methyl-5,6-dihydroxy indole 13(T)^(II) 2,3-dimethyl-5,6-dihydroxyindole 14(T)^(II) 5-methoxy-6-hydroxy indole 15(T)^(II)5-acetoxy-6-hydroxy indole 16(T)^(II) 5,6-diacetoxy indole 17(T)^(II)5,6-dihydroxy indole carbonic acid

Compositions 18(T)^(III) to 20(T)^(III) are identical to compositions1(T), with the proviso that monobromohydrate of 5,6-dihydroxy indolineis replaced by a compound T^(III).

compositions compound T^(III) 18(T)^(III) 5,6-dihydroxy indoline19(T)^(III) 1-methyl-5,6-dihydroxy indoline 20(T)^(III)1-ethyl-5,6-dihydroxy indoline

EXAMPLE 24

Dying compositions possessing pH 9.8 are prepared by mixing identicalpercentages of weight of a hydrogen peroxide solution (6% by weight) anda oxidative precursor dye composition prepared as given below in table1:

TABLE 1 Oxidative precursor dye composition (contents in percentage byweight) Oxidative dye compositions 1(V) 2(V) 3(V) 4(V)2,5,6-Triamino-4-hydroxypyrimidine 0.01 0.2 0.2 0.01 sulphate4-Amino-2-hydroxytoluene 0.5 0.5 2,5-Diaminotoluene sulphate 0.55 0.70.7 0.55 *common dye support 4-Chlororesorcine 0.17 0.17 Resorcine 0.050.05 Ascorbic acid 0.5 0.5 Cationic dye * in % by weight 1.0 1.03-Aminophenol 0.03 0.03 Demineralized water qs. 100 100 100 100 for forfor for *common dye support 1(V) 2(V) 3(V) 4(V) Cetylstearylalcohol11.00 11.00 Oleth-5 5.0 5.00 Oleic acid 2.5 10.0 10.0 2.50 Stearic acidmonoethanolamide 2.5 2.50 Coco fatty acid monoethanolamide 2.5 2.5Sodium laurylsuphate 1.7 1.7 Sodiumsulphite 1.0 1.00 1.00 1.001,2-Propanediol 1.0 1.00 Ammoniumchloride 0.5 0.50 EDTA, Tetrasodiumsalt0.2 0.20 Perfume 0.4 0.40 Comproteinhydrolysate 0.2 0.20 Silica 0.1 0.10*Cationic dye is mixed with the other components of the oxidative dyecomposition shortly before the applying to the hair. *Cationic dye is asingle cationic dye or composition of cationic dyes as given abovecompositions (V^(I)) = compositions (V^(I)) = composition 4(V) +composition 3(V) + *cationic dye *cationic dye Cationic dye of example 110(V^(I)) 10(V^(I))^(I) Cationic dye of example 2 11(V^(I))11(V^(I))^(I) Cationic dye of example 3 12(V^(I)) 12(V^(I))^(I) Cationicdye of example 4 13(V^(I)) 13(V^(I))^(I) compositions (V^(I)) =composition 4(V) + *cationic dye + dye** (*cationic dye/**dye in aration of 1:1) cationic cationic cationic cationic dye of dye of dye ofdye of dye** example 1 example 2 example 3 example 4 HC Yellow 214(V^(I)) 15(V^(I)) 16(V^(I)) 17(V^(I)) HC Yellow 4 18(V^(I)) 19(V^(I))20(V^(I)) 21(V^(I)) HC Yellow 6 22(V^(I)) 23(V^(I)) 24(V^(I)) 25(V^(I))Basic Yellow 57 26(V^(I)) 27(V^(I)) 28(V^(I)) 29(V^(I)) Basic Yellow 930(V^(I)) 31(V^(I)) 32(V^(I)) 33(V^(I)) Disperse Orange 3 34(V^(I))35(V^(I)) 36(V^(I)) 37(V^(I)) HC Red 3 38(V^(I)) 39(V^(I)) 40(V^(I))41(V^(I)) HC Red BN 42(V^(I)) 43(V^(I)) 44(V^(I)) 45(V^(I)) Basic Red 7646(V^(I)) 47(V^(I)) 48(V^(I)) 49(V^(I)) Basic Red 2 50(V^(I)) 51(V^(I))52(V^(I)) 53(V^(I)) Basic Violet 14 54(V^(I)) 55(V^(I)) 56(V^(I))57(V^(I)) Basic Blue 3 58(V^(I)) 59(V^(I)) 60(V^(I)) 61(V^(I)) BasicBlue 6 62(V^(I)) 63(V^(I)) 64(V^(I)) 65(V^(I)) Basic Blue 7 66(V^(I))67(V^(I)) 68(V^(I)) 69(V^(I)) Basic Blue 9 70(V^(I)) 71(V^(I)) 72(V^(I))73(V^(I)) Basic Blue 12 74(V^(I)) 75(V^(I)) 76(V^(I)) 77(V^(I)) BasicBlue 26 78(V^(I)) 79(V^(I)) 80(V^(I)) 81(V^(I)) HC Blue 2 82(V^(I))83(V^(I)) 84(V^(I)) 85(V^(I)) HC Blue 7 86(V^(I)) 87(V^(I)) 88(V^(I))89(V^(I)) HC Blue 12 90(V^(I)) 91(V^(I)) 92(V^(I)) 93(V^(I)) DisperseBlue 3 94(V^(I)) 95(V^(I)) 96(V^(I)) 97(V^(I)) HC Violet 1 98(V^(I))99(V^(I)) 100(V^(I)) 101(V^(I)) Disperse Violet 1 102(V^(I)) 103(V^(I))104(V^(I)) 105(V^(I)) Disperse Black 9 106(V^(I)) 107(V^(I)) 108(V^(I))109(V^(I)) Basic Brown 16 110(V^(I)) 111(V^(I)) 112(V^(I)) 113(V^(I))Basic Brown 17 114(V^(I)) 115(V^(I)) 116(V^(I)) 117(V^(I))2-amino-6-chloro-4- 118(V^(I)) 119(V^(I)) 120(V^(I)) 121(V^(I))nitrophenol 4-amino-2-nitrodiphenyl- 122(V^(I)) 123(V^(I)) 124(V^(I))125(V^(I)) amine-2′-carboxylic acid 6-nitro-1,2,3,4-tetra- 126(V^(I))127(V^(I)) 128(V^(I)) 129(V^(I)) hydroquinoxaline 4-N-ethyl-1,4-bis(2′-130(V^(I)) 131(V^(I)) 132(V^(I)) 133(V^(I)) hydroxyethylamino)-2-nitrobenzne hydrochloride 1-methyl-3-nitro-4-(2′- 135(V^(I)) 136(V^(I))137(V^(I)) 138(V^(I)) hydroxyethyl)- aminobenzene compositions (V^(I)) =composition 4(V) + *cationic dye*** (*cationic dye/***dye in a ration of1:1) cationic cationic cationic cationic dye of dye of dye of dye ofdye*** example 1 example 2 example 3 example 4 HC Yellow 2, HC Yel-139(V^(I)) 140(V^(I)) 141(V^(I)) 142(V^(I)) low 4 Basic Red 76, HC Red143(V^(I)) 144(V^(I)) 145(V^(I)) 146(V^(I)) BN, HC Red BN, Basic147(V^(I)) 148(V^(I)) 149(V^(I)) 150(V^(I)) Violet 14 Basic Blue 12,Basic 151(V^(I)) 152(V^(I)) 153(V^(I)) 154(V^(I)) Blue 64-N-ethyl-1,4-bis(2′- 155(V^(I)) 156(V^(I)) 157(V^(I)) 158(V^(I))hydroxyethylamino)-2- nitrobenzene hydrochloride, 6-nitro-1,2,3,4-tetrahydroquinoxaline Basic Brown 16, 159(V^(I)) 160(V^(I)) 162(V^(I))163(V^(I)) Disperse Black 9 compositions (V^(I)) = composition 4(V) +*cationic dye + dye**** (*cationic dye/****dye in a ration of 1:1)cationic cationic cationic cationic dye of dye of dye of dye of dyes****example 1 example 2 example 3 example 4 HC Yellow 2, HC Yel- 164(V^(I))165(V^(I)) 166(V^(I)) 167(V^(I)) low 4, Basic Red 2 Basic Red 76, HC Red168(V^(I)) 169(V^(I)) 170(V^(I)) 171(V^(I)) BN, Basic Red 2 HC Red BN,Basic Vio- 172(V^(I)) 173(V^(I)) 174(V^(I)) 175(V^(I)) let 14, DisperseViolet 1 Basic Blue 12, Basic 176(V^(I)) 177(V^(I)) 178(V^(I))179(V^(I)) Blue 6, Disperse Violet 1 2-amino-6-chloro-4- 180(V^(I))181(V^(I)) 182(V^(I)) 183(V^(I)) nitrophenol, 6-nitro-1,2,3,4-tetrahydro- quinoxaline, Basic Brown 17 Basic Brown 16, Dis-184(V^(I)) 185(V^(I)) 186(V^(I)) 187(V^(I)) perse Black 9, Basic Brown17 compositions (V^(I)) = composition 4(V) + *cationic dye + dye*****(*cationic dye/*****dye in a ration of 1:1) cationic cationic cationiccationic dye of dye of dye of dye of dye***** example 1 example 2example 3 example 4 HC Yellow 2, Basic Red 188(V^(I)) 189(V^(I))190(V^(I)) 191(V^(I)) 76, Basic Red 2, Dispense Orange 3 Basic Red 76,HC Red 192(V^(I)) 193(V^(I)) 194(V^(I)) 195(V^(I)) BN, Basic Red 2,Basic Violet 14 HC Red BN, Basic 196(V^(I)) 197(V^(I)) 197(V^(I))198(V^(I)) Violet 14, Dispense Violet 1, HC Red 3 Basic Blue 12, Basic199(V^(I)) 200(V^(I)) 201(V^(I)) 202(V^(I)) Blue 6, Disperse Violet 1,Basic Blue 9 2-amino-6-chloro-4- 203(V^(I)) 204(V^(I)) 205(V^(I))206(V^(I)) nitrophenol, 6-nitro- 1,2,3,4-tetrahydro- quinoxaline, BasicBrown 17, HC Red BN Basic Brown 16, 207(V^(I)) 208(V^(I)) 209(V^(I))210(V^(I)) Disperse Black 9, Basic Brown 17, Basic Red 76

Each of the oxidative precursor dye compositions 1(V), 2(V), 3(V) and4(V) are applied for 15 minutes to locks of bleached hair. The hair isthen not rinsed, but treated for 15 minutes with a oxidative precursordye compositions(V^(II)) which is prepared as given in table 2 below:

TABLE 2 oxidative precursor dye compositions (V^(II)) oxidativeprecursor dye compositions(V^(II)) oxidative precursor dye composition1(V) and 1(V^(II)) a cationic dye of example 1 as solution (1.0% byweight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 1(V) and 2(V^(II)) a cationic dye of example 2 as solution(1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 1(V) and 3(V^(II)) a cationic dye of example 3 as solution(1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 1(V) and 4(V^(II)) a cationic dye of example 4 as solution(1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 1(V) and a 4/14(V^(II)) to cationic dye composition(14(V^(II))-210(V^(II)) as solution 4/210(V^(II)) (1.0% by weight) withpH 9.8; in a ratio of 1:1 oxidative precursor dye composition 2(V) and5(V^(II)) a cationic dye of example 1 as solution (1.0% by weight) withpH 9.8; in a ratio of 1:1 oxidative precursor dye composition 2(V) and6(V^(II)) a cationic dye of example 2 as solution (1.0% by weight) withpH 9.8; in a ratio of 1:1 oxidative precursor dye composition 2(V) and7(V^(II)) a cationic dye of example 3 as solution (1.0% by weight) withpH 9.8; in a ratio of 1:1 oxidative precursor dye composition 2(V) and8(V^(II)) a cationic dye of example 4 as solution (1.0% by weight) withpH 9.8; in a ratio of 1:1 oxidative precursor dye composition 2(V) and a8/14(V^(II)) to cationic dye composition 14(V^(II))-210(V^(II)) assolution 8/210(V^(II)) (1.0% by weight) with pH 9.8; in a ratio of 1:1oxidative precursor dye composition 1(V) and 11(V^(II)) a cationic dyeof example 1 as solution (1.0% by weight) with pH 5 (adjusted withcitric acid); in a ratio of 1:1 oxidative precursor dye composition 1(V)and 12(V^(II)) a cationic dye of example 2 as solution (1.0% by weight)with pH 5 (adjusted with citric acid); in a ratio of 1:1 oxidativeprecursor dye composition 1(V) and 13(V^(II)) a cationic dye of example3 as solution (1.0% by weight) with pH 5 (adjusted with citric acid); ina ratio of 1:1 oxidative precursor dye composition 1(V) and 14(V^(II)) acationic dye of example 4 as solution (1.0% by weight) with pH 5(adjusted with citric acid); in a ratio of 1:1 oxidative precursor dyecomposition 1(V) and 14/14(V^(II)) to a cationic dye composition14(V^(II))-210(V^(II)) 14/210(V^(II)) solution (1.0% by weight) with pH5 (adjusted with citric acid); in a ratio of 1:1 oxidative precursor dyecomposition 2(V) and 15(V^(II)) a cationic dye of example 1 as solution(1.0% by weight) with pH 5 (adjusted with citric acid); in a ratio of1:1 oxidative precursor dye composition 2(V) and 16(V^(II)) a cationicdye of example 2 as solution (1.0% by weight) with pH 5 (adjusted withcitric acid); in a ratio of 1:1 oxidative precursor dye composition 2(V)and 17(V^(II)) a cationic dye of example 3 as solution (1.0% by weight)with pH 5 (adjusted with citric acid); in a ratio of 1:1 oxidativeprecursor dye composition 2(V) and 18(V^(II)) a cationic dye of example4 as solution (1.0% by weight) with pH 5 (adjusted with citric acid); ina ratio of 1:1 oxidative precursor dye composition 2(V) and18/14(V^(II)) to a cationic dye composition 14(V^(II))-210(V^(II)) assolution 18/210(V^(II)) (1.0% by weight) with pH 5 (adjusted with citricacid); in a ratio of 1:1 oxidative precursor dye composition 3(V)19(V^(II)) with pH 5 (adjusted with citric acid) oxidative precursor dyecomposition 4(V) 20(V^(II)) with pH 5 (adjusted with citric acid)oxidative precursor dye composition 3(V) 20/14(V^(II)) to comprisingcationic dye composition 14(V^(II))- 20/210(V^(II)) 210(V^(II)) with pH5 (adjusted with citric acid) oxidative precursor dye composition 4(V)21/14(V^(II)) to comprising cationic dye composition 14(V^(II))-21/210(V^(II)) 210(V^(II)) with pH 5 (adjusted with citric acid)cationic dye of example 1 in a watery citric gel (12.5% by 22(V^(II))weight) with pH 5; in an equimolar weight portion to the weight ofcomposition 3(V) cationic dye of example 2 in a watery citric gel (12.5%by 23(V^(II)) weight) with pH 5; in an equimolar weight portion to theweight of composition 3(V) cationic dye of example 3 in a watery citricgel (12.5% by 24(V^(II)) weight) with pH 5; in an equimolar weightportion to the weight of composition 3(V) cationic dye of example 4 in awatery citric gel (12.5% by 25(V^(II)) weight) with pH 5; in anequimolar weight portion to the weight of composition 3(V) cationic dyecomposition 14(V^(II))-210(V^(II)) a watery citric 25/14(V^(II)) to gel(12.5% by weight) with pH 5; in an equimolar weight 25/210(V^(II))portion to the weight of composition 3(V) cationic dye of example 1 assolution (1.0% by weight) 26(V^(II)) with pH 9.8; in an equimolar weightportion to composition 3(V) cationic dye of example 2 as solution (1.0%by weight) 27(V^(II)) with pH 9.8; in an equimolar weight portion tocomposition 3(V) cationic dye of example 3 as solution (1.0% by weight)28(V^(II)) with pH 9.8; in an equimolar weight portion to composition3(V) cationic dye of example 4 as solution (1.0% by weight) 29(V^(II))with pH 9.8; in an equimolar weight portion to composition 3(V) cationicdye composition 14(V^(II))-210(V^(II)) as solution 29/14(V^(II)) to(1.0% by weight) with pH 9.8; in an equimolar weight 29/210(V^(II))portion to composition 3(V)

Each of the oxidative precursor dye compositions 3(V) and 4(V) areapplied for 15 minutes to locks of bleached hair. The hair is then notrinsed, but treated for 15 minutes with a oxidative precursor dyecompositions(V^(II)) which is prepared as given in table 3 below:

TABLE 3 oxidative precursor dye compositions(V^(II)) oxidative precursordye compositions(V^(II)) oxidative precursor dye compositions 2(V) withpH 9.8; in a 9(V^(II)) ratio of 1:1 oxidative precursor dye compositions1(V) with pH 9.8; in a 10(V^(II)) ratio of 1:1

Then the hair is rinsed, washed with a standard shampoo and afterwardsdried.

The hair is dyed in a brilliant shades with very good enduranceproperties with respect to subsequent shampooing and fastness to rubbingand lightness.

EXAMPLE 25

Example 25 is identical to example 24 with the proviso that the dyingcompositions do not possess pH 9.8, but pH 5(pH value is adjusted withcitric acid).

EXAMPLE 26

Example 26 is identical to example 24 with the proviso that theoxidative precursor dye compositions (V^(II)) are replaced by theoxidative precursor dye compositions (W^(II)) which are prepared asgiven in table 1 below.

TABLE 1 dye compositions (W^(II)) Oxidative precursor dye compositions1(W^(II)) and hydrogen 1(W^(II)) peroxide solution (6% by weight); withpH 5 (adjusted with citric acid); in a ratio of 1:1 Oxidative precursordye compositions 2(W^(II)) and hydrogen 2(W^(II)) peroxide solution (6%by weight); with pH 9.8; in a ratio of 1:1 Oxidative precursor dyecompositions 1(W^(II)) and hydrogen 3(W^(II)) peroxide solution (6% byweight); with pH 9.8; in a ratio of 1:1 Oxidative precursor dyecompositions 2(W^(II)) and hydrogen 4(W^(II)) peroxide solution (6% byweight); with pH 5; in a ratio of 1:1 Cationic dye of example 1 (1.0% byweight) in a watery citric 5(W^(II)) gel (12.5% by weight) with pH 5; ina ratio of weight of 1:1 to composition 3(W^(II)) Cationic dye ofexample 2 (1.0% by weight) in a watery citric 6(W^(II)) gel (12.5% byweight) with pH 5; in a ratio of weight of 1:1 to composition 3(W^(II))Dye of example 4 with pH 9.8; in a ratio of weight of 1:1 to 7(W^(II))composition 3(W^(II)) Dye of example 4 ) with pH 9.8 and hydrogenperoxide solution 8(W^(II)) (6% by weight); in a ratio of weight of 1:1to composition 3(W^(II)) Cationic dye of example 3 (1.0% by weight) in awatery citric 9(W^(II)) gel (12.5% by weight) and hydrogen peroxidesolution (6% by weight); with pH 5 (adjusted with citric acid); in aratio of 1:1 Cationic dye of example 3 (1.0% by weight) in a waterycitric 10(W^(II)) gel (12.5% by weight) with pH 5; in a ratio of weightof 1:1 to composition 3(W^(II)) Cationic dye of example 4 (1.0% byweight) in a watery citric 11(W^(II)) gel (12.5% by weight) with pH 5;in a ratio of weight of 1:1 to composition 3(W^(II))

Then the locks of bleached hair is treated till of 7 is adjusted. After15 minutes at pH 7 the hair is rinsed, washed with a standard shampooand then dried.

The hair is dyed in a brilliant red-tinged violet shade with very goodendurance properties with respect to subsequent shampooing and fastnessto rubbing and lightness.

EXAMPLE 27

Example 27 is identical to example 26 with the proviso that theoxidative precursor dye compositions (W^(II)) are applied to the locksof bleached hair by a comb.

EXAMPLE 28

Example 28 is identical to example 25 with the proviso that theoxidative precursor dye compositions are applied to the locks ofbleached hair by a comb.

EXAMPLES 29-32

-   Example 29 is identical to example 24, and-   Example 30 is identical to example 25, and-   Example 31 is identical to example 26, and-   Example 32 is identical to example 27, and-   Example 33 is identical to example 28,-   with the proviso that the dying concerns not “locks of bleached    hair”, but “locks of middle blonde hair”.

EXAMPLES 33-37

-   Example 33 is identical to example 24, and-   Example 34 is identical to example 25, and-   Example 35 is identical to example 26, and-   Example 38 is identical to example 27, and-   Example 37 is identical to example 28, with the proviso that the    dying concerns not “locks of bleached hair”, but “bleached hair”.

EXAMPLES 38-42

-   Example 38 is identical to example 24, and-   Example 39 is identical to example 25, and-   Example 40 is identical to example 26, and-   Example 41 is identical to example 27, and-   Example 42 is identical to example 28, with the proviso that the    dying concerns not “locks of bleached hair”, but “middle blonde    hair”.

All of the forgoing examples can also be carried out without the use ofa common dye support.

In all of the forgoing examples the identified common dye support can bereplaced by the following dye support:

(*) Common dye support Ethanol 20.0 g Poly (C₈-C₁₆)alkylglucoside as anaqueous solution 4.8 g containing 60% active material (A.M.) bufferedwith ammonium citrate (0.5%), sold under the name Oramix CG110 ® by thecompany SEPPIC pH agent Qs pH = 8.5or by

In all of the forgoing examples the identified common dye support can bereplaced by the following dye support:

Common dye support Ethanol 20.0 g Nonylphenoloxyethylen with 9 moloxyethylen 8.0 g acid under the name IGEPAL NR 9 Or by the companyRHODIA CHEMIE 2-Amino-2-methyl-1-propanol qs. ph = 8.0or by

Common dye support Oleic acid 10.0 Sodiumsulphite 1.00

1. A cationic reactive dye which is a) an acridine of formula

wherein R₇ is hydrogen or C₁-C₄alkyl, An is an anion: and n⁻ is thecharge on the anion and is an integer from −1 to −6, b) an anthraquinoneof formula

wherein R₁₄ is —S—(C₁-C₄)—⁺NR₇R₈R₉ An^(n−), and An and n⁻ are as definedabove, and R₈ and R₉ are each independently of the others hydrogen orC₁-C₄alkyl; c) an azine of formula wherein R₇, n⁻ and An are as definedabove; d) an azo compound of formula

wherein U is —O—, —S— or —NR₁₇—, T is —CH═, —CR₁₇═or —N═, R₁₇ and R₁₉are each independently of the other C₁-C₄alkyl unsubstituted orsubstituted by OH, C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylaminoor by di-C₁-C₄alkylamino, R₁₈ is hydrogen, C₁-C₄alkyl, chlorine ornitro, R₂₀ is hydrogen, C₁-C₄alkyl, chlorine, nitro, amino,C₁-C₄monoalkylamino or di-C₁-C₄alkyl-amino, K is the radical of acoupling component from the aniline or phenol series or the radical of aheterocyclic coupling component, and n⁻ and An are as defined above; d′)an azomethine of formula

wherein R₃₀ is hydrogen, C₁-C₄alkyl or CN, R₂₉ is C₁-C₄alkylunsubstituted or substituted by OH or by CN, R₂₆ is hydrogen orC₁-C₄alkyl, R₂₇ and R₂₈ are each independently of the other hydrogen,C₁-C₄alkyl or C₁-C₄alkoxy, or R₂₇ is fluorine in the ortho position,with R₃₀ and R₂₈ being hydrogen and R₂₉ and R₂₆ being methyl, or R₂₇ ischlorine in the para position, with R₃₀ and R₂₈ being hydrogen and R₂₉and R₂₆ being methyl, or R₂₆ and R₂₇ together with the nitrogen andcarbon atoms bonding them form a 5- or 6-membered ring, and n⁻ and Anare as defined above; e) a dioxazine of formula

wherein B is a fibre-reactive group of formula (2a), (2b) (2c), (2d),(2e), (2f) or (2g),

wherein R₃ is —OSO₃X, —OSO₃ ⁻ or —Cl, R₄ and R₅ are each independentlyof the other —Cl or —Br, and R₁ and R² are each independently of theother —Cl, —F, or the radical of a compound of formula (3a), (3b), (3c),(3d), (3e), (3f) or (3g),

wherein R₆ is SO₃ ⁻, SO₃X, O⁻, OX, COO⁻, COOX or ⁺N(R₇R₈R₉)An⁻, X ishydrogen or a cation of an alkali metal or alkaline earth metal, R₇, R₈,R₉ and are each independently of the others hydrogen or C₁-C₄alkyl, R₁₀is COO⁻ or COOX, B′ is B or hydrogen, and R₃₁ is hydrogen, halogen,C₁-C₂₄alkyl or E, and n⁻ and An are as defined above; or a dioxazine offormula

wherein R₃₁, R₃₂ and R₃₃ are each independently of the others hydrogen,halogen, C₁-C₄alkyl, C₁-C₄-alkoxy or E, and n⁻ and An are as definedabove; f) a methine of formula

wherein R₂₉, R₃₀, n⁻ and An are as defined above and K₁, is the radicalof an aromatic or heterocyclic amine; or g) an oxazine of formula

wherein R₃₈ and R₃₉ are each independently of the other E, C₁-C₄alkyl orC₁-C₄alkoxy, and n⁻, n⁺ and An are as defined above; and, in theabove-mentioned formulae, E is in each case (D_(m)—E′), wherein D is—NR—, —(NR′—(C₁-C₇alkylene)-NR″)— or a piperazinylene of formula

wherein R is hydrogen, C₁-C₄alkyl, —CO—C₁-C₄alkyl, —CO-phenyl, ortho-,meta- or para-(C₆H₄(C₁-C₄-alkyl), ortho-, meta- orpara-(C₈H₄)—(C₁-C₄alkylene)-⁺N(R₇R₈R₉), or —(C₁-C₄alkyl)-⁺N(R₇R₈R₉),wherein R₇, R₈ and R₉ are each independently of the others hydrogen orC₁-C₄alkyl, and R′ and R″ are each independently of the other hydrogenor C₁-C₄alkyl, m is an integer 0 or 1, and E′ is hydrogen or B, with theproviso that E in each formula is at least once (D_(m)—E′) wherein E′ isB, and B is as defined above.
 2. A cationic reactive dye of formula (4d)or (4e)

wherein U is —O—, —S—or —NR₁₇—, T is —CH═, —CR₁₇=or —N═, R₁₇ and R₁₉ areeach independently of the other C₁-C₄alkyl unsubstituted or substitutedby OH, C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylamino or bydi-C₁-C₄alkylamino, R₁₈ is hydrogen, C₁-C₄alkyl, chlorine or nitro, R₂₀is hydrogen, C₀-C₄alkyl, chlorine, nitro, amino, C₁-C₄monoalkylamino ordi-C₁-C₄alkyl-amino, K is the radical of a coupling component from theaniline or phenol series or the radical of a heterocyclic couplingcomponent, n⁻ is the charge of the anion and is an integer from −1 to−6, and An is an anion,

wherein the radicals —K—E together form a compound of the formulae givenbelow

wherein R₁₉ is hydrogen or B, or C₁-C₄alkyl unsubstituted or substitutedby E, OH, C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylamino or bydi-C₁-C₄alkylamino, R₂₁ and R₂₂ are each independently of the other E,OH, C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylamino or bydi-C₁-C₄alkylamino, or C₁-C₄alkyl unsubstituted or substituted by E, OH,C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylamino or bydi-C₁-C₄alkylamino, R₂₃ and R₂₄ are each independently of the otherhydrogen or B, or C₁-C₄alkyl unsubstituted or substituted by OH,C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylamino or bydi-C₁-C₄alkylamino, or R₂₃ and R₂₄ together with the nitrogen atombonding them form a 5- or 6-membered ring unsubstituted or substitutedby E, or R₂₁ and R₂₃ together with the nitrogen and carbon atoms bondingthem form a 5- or 6-membered ring unsubstituted or substituted by E, orR₂₂ and R₂₄ together with the nitrogen and carbon atoms bonding themform a 5- or 6-membered ring unsubstituted or substituted by E, and R₂₅is hydrogen or B, or C₁-C₄alkyl unsubstituted or substituted by E, OH,C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylamino or bydi-C₁-C₄alkylamino, and E is in each case (D_(m)—E′), wherein D and mare as defined in claim 1, and E′ is hydrogen or B, with the provisothat E in each formula is at least once (D_(m)—E′) wherein E′ is B, andB has the definitions or preferences given in claim
 1. 3. A cationicreactive dye according to of formula (4d) or (4e),

wherein U is —O—, —S— or —NR₁₇—, T is —CH═, —CR₁₇═ or —N═, R₁₇ and R₁₉are each independently of the other C₁-C₄alkyl unsubstituted orsubstituted by OH, C₁-C₄alkoxy, halogen, CN, amino, C₁-C₄monoalkylaminoor by di-C₁-C₄alkylamino, R₁₈ is hydrogen, C₁-C₄alkyl, chlorine ornitro, R₂₀ is hydrogen, C₁-C₄alkyl, chlorine, nitro, amino,C₁-C₄monoalkylamino or di-C₁-C₄alkyl-amino, K is the radical of acoupling component from the aniline or phenol series or the radical of aheterocyclic coupling component, n⁻ is the charge of the anion and is aninteger from −1 to −6, and An is an anion, wherein the radicals —K—Edenote a compound of the formulae given below

wherein R₁₉ is hydrogen or B, or unsubstituted C₁-C₄alkyl, R₂₁ and R₂₂are each independently of the other hydrogen, E, unsubstitutedC₁-C₄alkyl, C₁-C₄alkoxy or halogen, R₂₃ and R₂₄ are each independentlyof the other hydrogen or B, or unsubstituted C₁-C₄alkyl, or R₂₃ and R₂₄together with the nitrogen atom bonding them form a pyrrolidine,piperidine, morpholine or piperazine ring unsubstituted or substitutedby E, or R₂₁ and R₂₃ together with the nitrogen atom and carbon atombonding them form a pyrrolidine, piperidine, morpholine or piperazinering unsubstituted or substituted by E, or R₂₂ and R₂₄ together with thenitrogen atom and carbon atom bonding them form a pyrrolidine,piperidine, morpholine or piperazine ring unsubstituted or substitutedby E; and E is in each case (D_(m)—E′), wherein D and m are as definedin claim 1, and E′ is hydrogen or B, with the proviso that E in eachformula is at least once (D_(m)—E′) wherein E′ is B, and B has thedefinitions or preferences given in claim
 1. 4. A cationic reactive dyeof formula (4i) or (4j),

wherein R₂₉, R₃₀, n⁻ and An are as defined in claim 1 and K₁ is theradical of an aromatic or heterocyclic amine; wherein the radicals —K₁—Edenote a compound of the formulae given below

wherein R₂₁ is E, C₁-C₄alkyl, C₁-C₄alkoxy or halogen, R₂₃ and R₂₅ areeach independently of the other hydrogen or B, or C₁-C₄alkylunsubstituted or substituted by OH, C₁-C₄alkoxy, halogen, CN, amino,C₁-C₄monoalkylamino or by di-C₁-C₄alkylamino, and E is in each case(D_(m)—E′), wherein D and m are as defined in claim 1, and E′ ishydrogen or B, with the proviso that E in each formula is at least once(D_(m)—E′) wherein E′ is B, and B has the definitions or preferencesgiven in claim
 1. 5. A cationic reactive dye according to claim 1 offormula

wherein R₂₁ and R₂₂ are each independently of the other hydrogen,C₁-C₄alkyl, C₁-C₄alkoxy or halogen, R₂₃ is hydrogen or unsubstitutedC₁-C₄alkyl, R₂₉ is C₁-C₄alkyl unsubstituted or substituted by OH or byCN, and R₃₀ is hydrogen, C₁-C₄alkyl or CN, n⁻ is the charge of the anionand is an integer from −1 to −6, and An is an anion, or a cationicreactive dye of formula

wherein R₁₇ and R₄₀ are each independently of the other hydrogen, orC₁-C₄alkyl unsubstituted or substituted by OH, C₁-C₄alkoxy, halogen, CN,amino, C₁-C₄monoalkylamino or by di-C₁-C₄-alkylamino, and An and n⁻, R₂₁and R₂₂ are as defined above, or a cationic reactive dye of formula

wherein An, n⁻, R₁₇, R₄₀, R₂₁, R₂₂ and R₂₃ are as defined above, and R₄₀and R₄₁ are each independently of the other hydrogen, or C₁-C₄alkylunsubstituted or substituted by OH, C₁-C₄alkoxy, halogen, CN, amino,C₁-C₄monoalkylamino or by di-C₁-C₄-alkylamino, or a cationic reactivedye of formula R₄₀ and R₄₁ are each independently of the other hydrogen,or C₁-C₄alkyl unsubstituted or substituted by OH, C₁-C₄alkoxy, halogen,CN, amino, C₁-C₄monoalkylamino or by di-C₁-C₄-alkylamino, or a cationicreactive dye of formula

wherein R₁₇, R₂₁, R₂₂, R₄₀, An and n⁻ are as defined above.
 6. A processfor the preparation of a cationic reactive dye according to claim 1, inwhich process a cationic chromophore is reacted with x fibre-reactivegroups B, wherein A, B, x and m are as defined in claim
 1. 7. A dyecomposition comprising a cationic reactive dye according to claim 1 anda further additive.
 8. A method of dyeing keratin-containing fibres,which comprises treating the fibres with a cationic reactive dyeaccording to claim
 1. 9. A method of dyeing hair, which comprisestreating the hair with an acidic or alkaline permanent-wave solution,and then with a composition comprising a cationic reactive dye accordingto claim
 1. 10. A method of dyeing hair, which comprises treating thehair with a) a mixture of an acidic or alkaline permanent-wave solutioncomprising a thiol derivative and b) a composition comprising a cationicdichlorotriazine reactive dye or a cationicmonofluoromonochloropyrimidine reactive dye according to claim
 1. 11. Amethod of dyeing keratin, wool, leather, silk, cellulose or polyamides,which comprises dyeing them with a tinctorially effective amount of acationic reactive dye according to claim
 1. 12. A method according toclaim 11 wherein hair is dyed.
 13. A method of dyeing keratin, wool,leather, silk, cellulose or polyamides, which comprises dyeing them witha tinctorially effective amount of a dye composition according to claim7.
 14. A method according to claim 13 wherein hair is dyed.